CN1083460C - Production process of cross-linked polyaspartic acid resin - Google Patents

Abstract

A process is disclosed for producing with good productivity a cross-linked polyaspartic acid resin having biodegradability and high water absorbency. The process features include one of the following steps: (a) a polysuccinimide, which has been brought into a dispersed state by a dispersant, and a cross-linking agent are reacted to produce the cross-linked polyaspartic acid resin; (b) imide rings of a cross-linked polysuccinimide are subjected to a hydrolysis reaction while controlling a swelling degree of a resulting gel, whereby the cross-linked polyaspartic acid resin is produced; and (c) a gel of a cross-linked polysuccinimide, which has been obtained by reacting a cross-linking agent to a solution of a polysuccinimide in an organic solvent, is disintegrated to subject imide rings of the cross-linked polysuccinimide to a hydrolysis reaction, so that the cross-linked polyaspartic acid resin is produced. The process may also include one or both of the following steps as needed: (d) a gel of the cross-linked polyaspartic acid resin is washed with water and/or a water-miscible organic solvent; and (e) the polysuccinimide is produced using a basic amino acid as a cross-linking agent.

Description

The production method of cross-linked poly-aspartic acid resin

The present invention relates to the method that a kind of production has the cross-linked poly-aspartic acid resin of (biology) degradation capability and high-hydroscopicity, the present invention also relates to the method for a kind of production simultaneously as the crosslinked polysuccinimide of cross-linked poly-aspartic acid resin precursor.

Superabsorbent polymer is a kind ofly can absorb water tens times to several thousand times to the resin of own wt, is used in health product, as sanitary towel and disposable diaper, also is used for other various fields simultaneously.

The known example that is applied to this superabsorbent polymer comprises crosslinked polyacrylic part neutralized reaction product (the open No.55-84304 of JP, U.S.Pat.No.4,625,001), the partial hydrolysate of starch-acrylonitrile copolymer (the open 46-43995 of JP), starch-acrylate graft copolymer (the open 51-125468 of JP), the hydrolysate of vinyl acetate-acrylate multipolymer (the open 52-14689 of JP), 2-acrylamido-2-methyl propane sulfonic acid and acrylic acid cross-linking copolymer (EP0068189), cross-linked polymer (the U.S.Pat.No.4 of cationic monomer, 906,717), and the hydrolysate of crosslinked iso-butylene-copolymer-maleic anhydride (U.S.Pat.No.4,389,513).

Yet consequent problem is, can not degrade during the processing of these superabsorbent polymers after use.

In this case, these superabsorbent polymers are generally by burning or recycling.But should be pointed out that except when burning, producing heat and damage the reason of incinerator material that the processing in the incinerator is a reason of Global warming and acid rain.On the other hand, the problem of following recycling is as being made the poor stability that reclaims slag by the bulky and nondegradation of plastics, and the serious problems that are faced with are to no longer include the place of many suitable recovery.

Say that further these polymkeric substance have poor degradation capability, remain in the water or in the soil semipermanently.Viewpoint from environment protection; their processing exists serious problem; for example; when the polymer treatment that is caused by health product such as disposable diaper and sanitary towel, their recovery is if carry out; the cost that needs are a large amount of; if and burn, based on its contained enormous amount, must have influence on global environment.In addition, it is reported that use crosslinked polyacrylic resin to cause the formation of complex compound as agricultural and gardening water holding material, this complex compound has as Ca in soil ²⁺Polyvalent ion and form a kind of insoluble layer [Matsumoto et al., KOBUNSHI (High Polymer, Japan), 42, August, 1993].It is believed that this layer self has hypotoxicity, but do not find fully at occurring in nature.The influence that the ecosystem produces is also known nothing medium-term and long-term accumulation of soil about this kind polymkeric substance, therefore need once investigation completely.Thereby should take careful attitude to their use.Similarly, there are potential problems in non-ionic resin, promptly owing to its nondegradation is deposited in the soil, although they do not form complex compound.Therefore, they produce adverse influence to nature probably.

Further, these polymer resins use has highly toxic monomer to human body skin etc., has done a large amount of work to eliminate the monomer that these come from polymerisate, is difficult but eliminate fully, for plant-scale product, the difficulty of expection is bigger especially.

[technical background] with superabsorbent polymer of biodegradability

On the other hand, biological degradation polyalcohol is just causing people's interest in recent years as " earth-compatible material ".They also are proposed as superabsorbent polymer.

The known example that is used for this biological degradation superabsorbent polymer, comprise crosslinked polyethylene oxide (the open 6-157795 of JP, Deng), crosslinked polyvinyl alcohol, crosslinked carboxymethyl cellulose (U.S.Pat.No.4,650,716), crosslinked alginic acid, crosslinked starch, and crosslinked polyamino acid.Wherein, crosslinked polyethylene oxide and crosslinked polyvinyl alcohol have low water absorbable rather than are especially suitable for use as the material that needs the high-hydroscopicity product, as health product, and disposable diaper, rag and paper handkerchief.

And these batchings only can be degraded by some specific bacterial classification, and therefore under normal conditions, their degradeds slowly or fully can not take place.In addition, when molecular weight is big, will greatly reduce its biodegradability.

In addition, crosslinked carbohydrate such as crosslinked carboxymethyl cellulose, crosslinked alginic acid, crosslinked starch contains a lot of firm hydrogen bonds in their molecule, have strong interaction between molecule and/or polymkeric substance.In view of the above, molecular chain can not be opened widely, and this just means that their water-absorbent is not very high.

[technical background of polyamino acid superabsorbent polymer]

On the other hand, can have biodegradability really, coordinate mutually with global environment simultaneously by the polymkeric substance that crosslinked polynary amino acid obtains.Now also find,, also can digest and absorb by the enzyme effect even they are absorbed by the body.And they do not show antigenicity in vivo, and its metabolite is nontoxic.Therefore, these polymkeric substance also are safe as a kind of material to the mankind.

As the disclosed example of this base polymer, a kind of method (comprise and use the gamma-ray irradiation poly-gamma-glutamic acid) of producing the high water absorbency polymer product, see report (the The Joural ofthe Society of Polymer Science in KOBUSHI RONBUNSHU such as Kunioka, Japan), 50 (10), 755 (1993).Yet, on the industrialization angle, be used for this technology ⁶⁰The Co irradiation system needs many equipment to shield ray, and its control is paid particular attention to, and therefore, this technology is impracticable.A long-range problem is, also must take into account as the high cost of the polyglutamic acid of raw material.

In addition, the method for obtaining hydrogel by the cross-linked acid acidic amino acid sees report, Akamatsu etc., U.S.Pat.No.3,948,863 (corresponding to JP kokoku 52-41309) and Iwatsuki etc., JP Kokai5-279416.Further, use crosslinked aminoacid polymers to see report as superabsorbent polymer, Sikes etc., JPPCT Kokai 6-506224 (corresponding to U.S.Pat.No.5247068 and U.S.Pat.No.5284936), Suzuki etc., JP Kokai 7-309943 and Harada etc., JP kokai 8-59820.

Yet in all above-mentioned reports, polymkeric substance does not all possess enough water-absorbents or inhales salt water-based and practicality.And consequent problem is that their gel has low intensity, becomes as time goes by and is clamminess.

Described at the open 7-224163 of JP special permission, the inventor discloses the technology that a kind of production has the absorbefacient cross-linked poly-aspartic acid resin of haline water, it comprises that a kind of linking agent of use and polysuccinimide react, then the imide ring of hydrolysed residue.

In addition, described at the open 9-169840 of JP special permission, the inventor also discloses the technology that a kind of production has the absorbefacient cross-linked poly-aspartic acid resin of haline water, it comprises crosslinked polysuccinimide, then, a kind of can with the tight mixed solvent of miscible organic solvent of water and water in, with the imide ring of hydrolysed residue.

For the earth-consistency and high suction, the cross-linked poly-aspartic acid resin that is obtained by these technology is very useful.Yet,, also have the part that has much room for improvement from industrialized angle.Specifically, the concentration of the cross-linked poly-aspartic acid resin of being produced by these production methods is low to moderate 5wt%, and this shows that it is still waiting to improve on volumetric efficiency.And according to the inventor's knowledge, in producing the cross-linked poly-aspartic acid resin process, the imide ring of hydrolytic crosslinking polysuccinimide will make resin suction and the swelling in the reaction system in water, thereby cause gelation significantly.This becomes difficult with regard to the stirring that makes reaction system.Hydrolysing agent can not disperse again, to such an extent as to reaction can not fully be carried out.Consequently so the cross-linked poly-aspartic acid resin of preparation does not have high-hydroscopicity.In addition, at organic solvent or contain and be hydrolyzed in the mixed solvent of organic solvent at high proportion and will make the reaction that only is hydrolyzed of resin in the reaction system, to such an extent as to that the speed of response of hydrolysis becomes is very low on the resin particle surface.This causes the cross-linked poly-aspartic acid resin of so preparation not have high-hydroscopicity equally.

The inventor finds that Zhi Bei cross-linked poly-aspartic acid resin contains water-soluble impurity such as water-soluble polymers and salt as mentioned above.Correspondingly, they have the part of having much room for improvement, as improve its gel-strength, remove the tackiness of gel surface, and improve the absorptivity to salt-containing solution.

In the production method of the open 7-224163 of JP, all the defective of the crosslinked polysuccinimide step of control production is that crosslinking reaction is carried out fully, therefore can not obtain to have the superabsorbent resin of high-hydroscopicity.According to the open disclosed production method of 9-169840 of JP, in the production stage of crosslinked polysuccinimide, resin is the absorption reaction solvent during crosslinking reaction, and this reaction system is cured thus.This makes and under agitation reacts very difficult, or the aftertreatment of reaction becomes very difficult.Therefore, this production method is not suitable for industrialized production., improve aspects such as control method and processing step thereof and be still waiting to improve such as simplification as the production method of the polysuccinimide of cross-linked poly-aspartic acid resin precursor.

In disclosed Japanese Patent JP7-224163 and JP9-169840, described and used basic aminoacids such as Methionin or the ornithine of polyamines, considered that from the residual unreacted linking agent and the security of degradation production this use is preferred as linking agent.Yet the alkaline polynary amino acid that particularly points out in these publications exists some problems, has low reactive behavior etc. as them, although use their ester can improve its reactive behavior, these esters itself are expensive.

General purpose of the present invention is further to improve inventor's invention disclosed.

Especially, first purpose of the present invention provides a kind of method, and this method can easily be prepared the cross-linked poly-aspartic acid resin with high-hydroscopicity with high volumetric efficiency by the imide ring in the hydrolytic crosslinking polysuccinimide.

Second purpose of the present invention provides a kind of method for preparing cross-linked poly-aspartic acid resin, and by remove water-soluble by product in the purification resin process, this resin has good gel-strength, improves the tackiness on the gel surface.

The 3rd purpose of the present invention provides and a kind ofly just can prepare method as the crosslinked polysuccinimide of cross-linked poly-aspartic acid resin precursor through easy steps.

The 4th purpose of the present invention provides a kind of method for preparing cross-linked poly-aspartic acid resin, wherein, in order to obtain to have the cross-linked poly-aspartic acid resin of excellent safety, basic aminoacids such as Methionin or ornithine are reacted effectively as the good linking agent of security.

First purpose can reach by the preparation method of cross-linked poly-aspartic acid resin, promptly, make the reaction that is hydrolyzed of imide ring in the crosslinked polysuccinimide, the resin swelling degree in reaction system of hydrolysis reaction wherein is controlled to be under 3～100 times the situation and carries out.

Can make the degree of resin gelization reach best, condition is, set hydrolysis reaction conditions Ru Shui and can with the ratio of water miscibles organic solvent, the concentration of salt and temperature are so that hydrolysis reaction carries out under 3～100 times of swelling capacity keeping.Consequently can accelerate hydrolysis rate, make hydrolysis reaction carry out fully.As a kind of result, obtain the cross-linked poly-aspartic acid resin that water-absorbent is improved.In addition, can also easily stir.This can increase the concentration of resin in the reaction system, thereby obtains than higher volumetric efficiency.

Second purpose can reach by the preparation method of cross-linked poly-aspartic acid resin, comprising water or can with the miscible organic solvent washing of water or the gel of redeposition charging cross-linked poly-aspartic acid resin.

Water or can obtain the cross-linked poly-aspartic acid resin that water-absorbent and gel-strength all are improved with miscible organic solvent washing of water or redeposition gel.It is believed that this owing to having removed the water-soluble component that is contained in the resin gel and is harmful to the living matter of resin, as monomer, oligopolymer, and inorganic or organic salt.

The 3rd purpose can reach by the preparation method of crosslinked polysuccinimide resin, comprises using linking agent and raw material polysuccinimide to react, and raw material polysuccinimide wherein is in dispersion state by a kind of dispersion agent.

When the above-mentioned raw material polysuccinimide that is in dispersed carries out crosslinking reaction, can omit the process control that to avoid excessive gelation, and make crosslinking reaction carry out finely.Therefore, can be by simple method, high yield ground obtains as the crosslinked polysuccinimide with (biology) degradation capability and high-hydroscopicity cross-linked poly-aspartic acid resin precursor.

First and the 3rd purpose also can reach by the preparation method of cross-linked poly-aspartic acid resin, comprise and decomposing owing in crosslinking reaction, contain organic solvent and the gel of the crosslinked polysuccinimide of agglomerative, the imide ring of reservation is hydrolyzed, although be very difficult before the hydrolysis of gel is sentenced.

The 4th purpose can realize by the preparation method of cross-linked poly-aspartic acid resin, comprise basic aminoacids such as Methionin or the ornithine of use as linking agent, with its carboxylate salt, the form of preferred as alkali or alkaline earth salt makes polysuccinimide carry out crosslinking reaction effectively.

Cross-linked poly-aspartic acid resin of the present invention can be compatible with global environment after using based on its biological degradability, and therefore, at disposable diaper, the aspects such as application on agricultural or the gardening are very useful as superabsorbent polymer.(1) structure of cross-linked poly-aspartic acid resin

Generally divide, polymkeric substance of the present invention is mainly by the basic skeleton portion branch of main chain, and pendant moiety and crosslink part are formed, and this three part will be described separately below.The main chain basic framework of [1-1] cross-linked poly-aspartic acid resin

The main chain basic framework of cross-linked poly-aspartic acid resin of the present invention can be separately that asparagicacid residue maybe can be the amino acid whose multipolymer of aspartic acid and non-aspartic acid.By way of parenthesis, in the present invention, no matter the form of its bonding how, the repeating unit of aspartic acid is referred to as " poly aspartic acid residue " in the polymkeric substance.

The amino acid object lesson of non-aspartic acid can comprise 19 kinds of essential amino acids except that aspartic acid, the L-ornithine, a-amino acid series, β-An Jibingsuan, γ-An Jidingsuan, neutral amino acids, acidic amino acid, ω-acidic amino acid ester, basic aminoacids, the basic amino acid derivant that N-replaces, aspartic acid-L-phenyl amino propionic acid dipolymer (aspartame); And thionamic acid such as L-cysteic acid.Each a-amino acid can or with optically active substance form (L-or D-) or with the racemic modification form.

And polymkeric substance can be the multipolymer that contains non-amino acid whose repeating unit.

The example of multipolymer repeating unit can be an aminocarboxylic acid, thionamic acid, aminophosphonic acid, hydroxycarboxylic acid, mercaptan carboxylic acid, sulfydryl sulfonic acid, dehydrating condensation products such as sulfydryl phosphonic acids.

Also comprise polyamines; polyvalent alcohol, polythiol, poly carboxylic acid; many sulfonic acid; polyphosphonic acid, many hydrazine compounds, polyamino formylation compound; many sulfonamides; many ammonia phosphono compound (polypHospHonamide), polyepoxy compound, polyisocyanate compound; the polythio isocyanate compound; many aziridine cpds, multiple-amino ester formate compound, polyamino formic acid cpds Duo oxazoline compound; the compound that contains multivalence reactive behavior unsaturated link(age), the hydration condensation product of polyvalent metal compounds etc., the derivative of adduct and replacement.

For multipolymer, it can be segmented copolymer or random copolymers, also can be graft copolymer.

Have no particular limits constituting poly aspartic acid residue number of repeating units, but based on the whole repeating unit numbers that constitute molecule, 1～99.8% be preferably that wherein 10～99.8% for more preferably.

As the repeating unit of cross-linked poly-aspartic acid resin main chain basic framework, from the angle of high-hydroscopicity is provided, they be preferably independent asparagicacid residue or with the multipolymer of L-glutamic acid or Methionin.From the angle of suitability for industrialized production, repeating unit by asparagicacid residue constitute separately for preferred especially.

Amido linkage on the poly aspartic acid main chain basic framework can be α-key or β-key.

That is to say, for poly aspartic acid or its multipolymer, α-key is by the α in the monomer of analogue in amino or the aspartic acid or multipolymer and the aspartic acid-the carboxyl bonding forms, and β-key is to be formed by the β in amino or analogue and the aspartic acid-carboxyl bonding.

This α-key and β-key are present in the poly aspartic acid usually together, and the para-linkage mode has no particular limits.

Side-chain radical among the present invention and crosslinked group are the carboxylic acid derivative that is formed by the replacement of hydroxy-acid group in the poly aspartic acid basically.Below will be described in detail them.The side-chain structure of [1-2] cross-linked poly-aspartic acid resin

Each side chain of cross-linked poly-aspartic acid resin has a kind of like this structure, and its formation is by hydrolysis the imide ring in the crosslinked polysuccinimide to be opened, and contains the carboxyl that hydrolysis forms.Cross-linked poly-aspartic acid resin can also contain other substituent side chain.This other substituent example can comprise and contains one or more hydroxyls, amino, and sulfydryl, carboxyl, sulfonic group, phosphonate group, alkyl, aryl, the side group of aralkyl etc., but be not limited to this.This side group can be not have substituent alkyl, aryl or aralkyl.These side groups pass through acid amides, ester, and keys such as thioesters link to each other with the poly aspartic acid residue.

Each carboxyl that forms by hydrolysis can the free form or the form of salt exist.The salifiable ionic object lesson of shape can comprise alkalimetal ion such as sodium, potassium and lithium ion; Ammonium ion such as ammonium, tetramethyl-ammonium, tetraethyl-amine, tetrapropyl ammonium, TBuA, four pentyl ammonium, tetrahexyl ammonium, ethyl trimethyl ammonium, trimethylammonium propyl ammonium, butyl trimethyl ammonium, the amyl group trimethyl ammonium, hexyl trimethyl ammonium, cyclohexyl trimethyl ammonium, benzyltrimethylammon.um, triethyl propyl ammonium, triethyl butyl ammonium, triethyl amyl group ammonium, triethyl hexyl ammonium, the ion of cyclohexyl triethyl ammonium and benzyl triethyl ammonium ammonium; Amine ion such as Trimethylamine, triethylamine, tripropylamine, tributylamine, three amylamines, three hexyl amines, trolamine, tripropanol amine, three butanolamines, three amylalcohol amine, three hexanol amine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, dicyclohexylamine, dibenzyl amine, ethylmethylamine, methyl-propyl amine, butyl methyl amine, methyl amyl amine, the methyl hexyl amine, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, the amine ion of amino dodecane and cetylamine.

In these ions, what those had little atom or molecular weight is preferred, and this is that the molecular weight of every monomeric unit correspondingly becomes greatly owing to the increase along with ionic atom or molecular weight, and the water-absorbent of per unit weight correspondingly diminishes.In the occasion that may come in contact with people's skin or analogue, wish that they have hypotoxicity, this just means sodium, and potassium, lithium, ammonium or trolamine are preferred, and from the angle of economy, use sodium, and potassium is for preferred especially.The structure of [1-3] cross-linked poly-aspartic acid resin crosslink part

For the cross-linked poly-aspartic acid resin crosslink part, their molecular structure is had no particular limits.The crosslink part of cross-linked poly-aspartic acid resin can be thought they each is divided into " bonding part " and " connection portion " of crosslinked this bonding part on the basic framework that is bonded to main polymer chain.The part of these divisions below will be described.Bonding part in [1-3-1] cross-linked poly-aspartic acid resin crosslink part

Bonding in the cross-linked poly-aspartic acid resin crosslink part is partly had no particular limits.Their object lesson can comprise respectively by amido linkage, the structure that ester bond and thioester bond form.Can only contain one type structure, also can contain the structure of compound type together.The connection portion of crosslink part on [1-3-2] cross-linked poly-aspartic acid resin

Connection portion to crosslink part on cross-linked poly-aspartic acid resin has no particular limits.Be the object lesson of this connection portion below.

-CH ₂-,-CH ₂CH ₂-,-CH ₂CH ₂CH ₂-,-CH ₂CH ₂CH ₂CH ₂-,-(CH ₂) ₅-,-(CH ₂) ₆-,-(CH ₂) ₇-,-(CH ₂) ₈-,-(CH ₂) ₉-,-(CH ₂) ₁₀-,-(CH ₂) ₁₁-,-(CH ₂) ₁₂-,-(CH ₂) ₁₃-,-(CH ₂) ₁₄-,-(CH ₂) ₁₅-,-(CH ₂) ₁₆-,-(CH ₂) ₁₇-,-(CH ₂) ₁₈-,-CH ₂CH ₂O-CH ₂CH ₂-,-(CH ₂CH ₂O) ₂CH ₂CH ₂-,-(CH ₂CH ₂O) ₃CH ₂CH ₂-,-(CH ₂CH ₂O) ₄CH ₂CH ₂-,-(CH ₂CH ₂O) ₅CH ₂CH ₂-,-(CH ₂CH ₂O) ₆-CH ₂CH ₂-,-CH ₂CH ₂CH ₂OCH ₂CH ₂CH ₂-,-(CH ₂CH ₂CH ₂O) ₂CH ₂CH ₂-CH ₂-, (CH ₂CH ₂CH ₂O) ₃CH ₂CH ₂CH ₂-, (CH ₂CH ₂CH ₂O) ₄CH ₂CH ₂CH ₂-, (CH ₂CH ₂CH ₂O) ₅CH ₂CH ₂CH ₂-, (CH ₂CH ₂CH ₂O) ₆CH ₂CH ₂CH ₂-,

With

These connection portions can non-replacement form or exist to be substituted the form that base replaces.Substituent representation example can comprise the linearity that contains 1～18 carbon atom or the alkyl of branching; The cycloalkyl that contains 3～8 carbon atoms; Aralkyl; The phenyl of replacement or non-replacement; The naphthyl of replacement or non-replacement; The alkoxyl group that contains the linearity or the branching of 1～18 carbon atom; Aralkoxy; Thiophenyl; Contain the linearity of 1～18 carbon atom or the alkylthio of branching; The alkylamino that contains the linearity or the branching of 1～18 carbon atom; Each alkyl is linearity or branching and dialkyl amido that contain 1～18 carbon atom; Each alkyl is linearity or branching and trialkyl ammonium that contain 1～18 carbon atom; Hydroxyl, amino, sulfydryl, carboxyl, sulfonic group and phosphonate group and its esters; Carbalkoxy; And alkyl carbonyl oxy.

Example can comprise alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl more specifically; Cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group; Aralkyl such as benzyl, styroyl, hydrocinnamyl and benzene butyl; Phenyl such as phenyl, tolyl, xylyl, chloro-phenyl-, and xenyl; Naphthyl such as naphthyl and methyl naphthyl; Alkoxyl group such as methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy, heptan the oxygen base, octyloxy, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, heptadecane oxygen base and octadecane oxygen base; Aralkoxy such as phenoxy group, benzyloxy and tolyloxy; Alkylthio such as sulphomethyl, thio-ethyl, sulfo-propyl group, the sulfo-butyl, sulfo-amyl group, sulfo-hexyl, the sulfo-heptyl, sulfo-octyl group, sulfo-nonyl, the sulfo-decyl, sulfo-undecyl, sulfo-dodecyl, the sulfo-tridecyl, sulfo-tetradecyl, sulfo-pentadecyl, the sulfo-hexadecyl, sulfo-heptadecyl and sulfo-octadecyl; Aryl alkylthio such as thio-phenyl, sulfo-benzyl and sulfo-tolyl; Alkylamino such as methylamino, ethylamino, propyl group amino, butyl amino, amyl group amino, hexyl amino, heptyl amino, octyl group amino, nonyl amino, decyl amino, undecyl amino, dodecyl amino, tridecyl amino, tetradecyl amino, pentadecyl amino, hexadecyl amino, the amino and octadecyl amino of heptadecyl; Dialkyl amido such as dimethylamino, diethylamino, dipropyl amino, dibutylamino, diamyl amino, dihexyl amino, diheptyl amino, dioctyl amino, dinonyl amino, didecyl amino, two-undecyl amino, two-dodecyl amino, two-tridecyl amino, two-tetradecyl amino, two-pentadecyl amino, two-hexadecyl amino, two-heptadecyl amino, two-octadecyl amino, ethylmethylamino and methyl-propyl amino; Trialkyl ammonium such as trimethylammonium ammonium, triethyl ammonium, tripropyl ammonium, tributyl ammonium, three amyl group ammoniums, three hexyl ammoniums, three heptyl ammoniums, trioctylphosphine ammonium, three nonyl ammoniums, three decyl ammoniums, three-undecyl ammonium, three-dodecyl ammonium, three-tridecyl ammonium, three-tetradecyl ammonium, pentatriacontane base ammonium, three-hexadecyl ammonium, three-heptadecyl ammonium, three-octadecyl ammonium, dimethyl ethyl ammonium, dimethyl benzyl ammonium and methyl dibenzyl ammonium; Hydroxyl, amino, sulfydryl, carboxyl, sulfonic group and phosphonate group and its esters; Alkoxy carbonyl such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl, pentyloxy carbonyl, hexyloxy carbonyl, heptan oxygen base carbonyl, carbonyl octyloxy, the ninth of the ten Heavenly Stems oxygen base carbonyl, the last of the ten Heavenly stems oxygen base carbonyl, undecyl oxygen base carbonyl, dodecyl oxygen base carbonyl, tridecyl oxygen base carbonyl, tetradecyl oxygen base carbonyl, pentadecyl oxygen base carbonyl, hexadecyl oxygen base carbonyl, heptadecyl oxygen base carbonyl and octadecyl oxygen base carbonyl; And alkyl carbonyl oxy such as methyl carbonyl oxygen base, ethyl oxy carbonyl, carbonyl propyl oxygen base, butyl carbonyl oxygen base, amyl group carbonyl oxygen base, hexyl carbonyl oxygen base, heptyl carbonyl oxygen base, octyl group carbonyl oxygen base, nonyl carbonyl oxygen base, decyl carbonyl oxygen base, undecyl carbonyl oxygen base, dodecyl carbonyl oxygen base, tridecyl carbonyl oxygen base, tetradecyl carbonyl oxygen base, pentadecyl carbonyl oxygen base, hexadecyl carbonyl oxygen base, heptadecyl carbonyl oxygen base and ten alkyl carbonyl oxies.

In these representative substituting groups, what those had small molecular weight is preferred, this be since select macromolecule cause that to have a molecular weight of the crosslink part of macromolecule and every repeating unit relatively large, and cause the water-absorbent of per unit weight less thus.Also preferably can make the substituting group of production process simplification simultaneously usually.For example, the connection portion of non-replacement or be substituted base (as methyl, ethyl, methoxyl group, methoxycarbonyl and/or methyl carbonyl oxygen base; Hydroxyl, amino, sulfydryl, carboxyl, sulfonic group and/or phosphonate group, and/or its esters) connection portion that replaces.

When cross-linked poly-aspartic acid resin was used as the water holding material, the resin that contains polar group in the molecule was for preferred.Correspondingly, for crosslink part, non-replacement and polar functionalities or contained that polar substituent (as hydroxyl, amino, sulfydryl, carboxyl, sulfonic group and/or phosphonate group, and/or its esters) replaces for preferred especially.

Although the ratio to these crosslink parts has no particular limits, there is crosslink part to carry thereon repeating unit, in quantitative terms, be preferably 0.1～20% of the whole repeating units of polymkeric substance, more preferably 0.5～10%.[2] preparation method of polysuccinimide

Although the preparation method to the non-crosslinked polysuccinimide of practical application in the present invention has no particular limits,, can mention 80,3361 et seq., the method that provides in 1958 grades as a concrete example at J.Amer.Chem.Soc..

The polysuccinimide molecular weight that uses is had no particular limits, but as a kind of water holding material, high molecular weight can obtain high ability.Its molecular weight is generally 30,000 or higher, and preferred 60,000 or higher, more preferably 90,000 or higher.

And polysuccinimide maybe can be that linear structure maybe can be a branched structure.[3] preparation method of crosslinked polysuccinimide

Although the preparation method to the crosslinked polysuccinimide of practical application in the present invention has no particular limits, but representative method can comprise the method that a kind of linking agent and polysuccinimide solution react in organic solvent, and a kind of method to be reacted by the polysuccinimide of dispersion agent dispersing morphology and linking agent.

Can be with reference to former method, for example, in disclosed Japanese Patent JP7-224163, in the presence of organic solvent, linking agent joined carry out crosslinking reaction in the polysuccinimide solution.When this crosslinking reaction reached a kind of high-crosslinking-degree, so just the form with gel obtained crosslinked polysuccinimide.This then gel is handled in the mode that after this will describe.

On the other hand, back one method is one of feature of the present invention.In the present invention promptly, can be at polysuccinimide that forms dispersed by dispersion agent and the reaction between the linking agent by simple technology, high productivity obtains crosslinked polysuccinimide.Poor solvent as dispersion agent is selected from the organic solvent that can not dissolve polysuccinimide basically fully, and water is preferred.

As the example of these class methods, the method for [3-1]～[3-5] below can mentioning, in these class methods, polysuccinimide forms dispersed by the poor solvent (as water and/or other poor solvent) as dispersion agent.

[3-1] polysuccinimide forms dispersed in the poor solvent as dispersion agent, then, react with linking agent.

[3-2] polysuccinimide is dissolved in the good solvent, preparation polysuccinimide solution.The poor solvent that this solution is used as dispersion agent mixes, so that polysuccinimide forms dispersed, then, reacts with linking agent.

The mixed solvent of [3-3] preparation good solvent and poor solvent is used as dispersion agent.Polysuccinimide is joined in this mixed solvent, form dispersed, then, react with linking agent.

[3-4] the first step is dissolved in the good solvent polysuccinimide with preparation polysuccinimide solution, toward wherein adding linking agent crosslinking reaction is partly carried out.Second step through the crosslinking reaction of the first step, before the polysuccinimide gelling, added poor solvent as dispersion agent so that polysuccinimide forms dispersed, further carried out crosslinking reaction.

[3-5] is dissolved in the good solvent polysuccinimide with preparation polysuccinimide solution, toward the poor solvent that wherein adds lentamente as dispersion agent, makes polysuccinimide form dispersed, reacts with linking agent then.

According to method [3-1], polysuccinimide forms dispersed in the poor solvent as dispersion agent.Polysuccinimide in the crosslinking reaction process is not both by dissolution with solvents, also not by solvent-swollen.In addition, the difference of method [3-2] is that polysuccinimide is once dissolved in good solvent, and the polysuccinimide solution of Sheng Chenging mixes with poor solvent as dispersion agent to disperse polysuccinimide then.In method [3-2], the polysuccinimide in the crosslinking reaction process exists with the form of dispersed, and is partly dissolved in good solvent or swelling.Therefore, [3-1] compares with method, and method [3-2] makes crosslinking reaction carry out more easily.And polysuccinimide has good dispersed, and this is because a dissolved polysuccinimide is disperseed by depositing well again.

In method [3-4], need before gelling, add poor solvent, in case this is because of the polysuccinimide gelling in the crosslinking reaction process, the dispersion of being undertaken by dispersion agent just becomes difficult.Randomly, before or after adding linking agent, for preventing gel, from slowing down the angle of crosslinking reaction, the poor solvent that can add appropriate amount is as acid or its analogue.And, the imide ring reaction that can be hydrolyzed in the first step and the crosslinked polysuccinimide in second step.

The object lesson that is used for method [3-1]～[3-5] poor solvent will be described following.In each method of [3-2]～[3-5], good solvent mixes use with poor solvent especially, so that these solvents have good mutual miscibility.[4] preparation condition of crosslinked polysuccinimide

The common preparation condition of aforesaid method [3-1]～[3-5] will be described following.The good solvent that [4-1] uses in crosslinking reaction

" good solvent " referred in this is interpreted as dissolving fully basically the organic solvent of polysuccinimide.

Have no particular limits being used for good solvent of the present invention, but usually those be used for the blended poor solvent have solubility for preferred.Usually the such good solvent of preferred use: promptly, the linking agent of use can dissolve basically.For example, when use has the linking agent of high-hydrophilic, has high polar mixed solvent for preferred.And when use had the high hydrophobicity linking agent, low polar mixed solvent was preferred.

The concrete example of good solvent can comprise N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), and sulforane.Wherein, N, dinethylformamide, N,N-dimethylacetamide is for more preferably, and this is because they have high resolution to polysuccinimide.These solvents can use or mix use separately.The poor solvent that [4-2] uses in the crosslinking reaction process

" poor solvent " referred in this is interpreted as can not dissolving fully basically the organic solvent and the water of polysuccinimide.Among the present invention, this poor solvent is suitable as dispersion agent.

Have no particular limits being used for poor solvent of the present invention.As long as can be used for the conventional chemical reaction and polysuccinimide is had low-solubility, any solvent all can use.When poor solvent was used for mixing with good solvent, those and good solvent had the poor solvent of solubility for preferred.As above-mentioned good solvent, the such poor solvent of preferred usually use: promptly, the linking agent of use can dissolve basically.

The object lesson of poor solvent can comprise water; Pure as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, octanol, 2-methyl cellosolve and cellosolvo; Dibasic alcohol such as ethylene glycol, glycol ether, triglycol, propylene glycol and dipropylene glycol; Glycosolves such as methyl glycosolves and ethyl glycosolves; Ketone such as acetone, methylethylketone and methyl iso-butyl ketone (MIBK); Cyclic ethers such as tetrahydrofuran (THF) and dioxane; Sherwood oil; Pentane; Hexane; Heptane; Octane; Hexanaphthene; Benzene; Toluene; Ethylbenzene; Dimethylbenzene; Naphthalane; Phenyl ether; Aniosole; And cresols.Water wherein, methyl alcohol, ethanol, propyl alcohol and Virahol are for preferred especially, and this is because they can dissolve linking agent or amino acid whose carboxylate salt.These solvents can be used alone or as a mixture.

By way of parenthesis, these poor solvents also can be used for other purpose except that disperseing polysuccinimide, for example, are used for reducing crosslinking reaction speed.The good solvent that [4-3] uses in crosslinking reaction and the mixture ratio of poor solvent

When good solvent mixes with poor solvent when using, their mixture ratio is had no particular limits.Use poor solvent will strengthen the effect of poor solvent with suitable vast scale, thus, polysuccinimide forms dispersed and can avoid gelation.On the other hand, use poor solvent will strengthen the effect of good solvent with suitable small proportion, thus, polysuccinimide forms uneven dispersed.And, use poor solvent with suitable small proportion, can reduce the expense of solvent recuperation usually, therefore, be useful from considering economically.

Above-mentioned good solvent and the poor solvent mentioned respectively uses such good solvent and poor solvent: when forming mixed solvent, linking agent is wherein dissolved substantially usually.The concentration of the polysuccinimide that [4-4] uses in crosslinking reaction

The concentration that is in the polysuccinimide of dispersed in the crosslinking reaction process is had no particular limits.But its preferred concentration is 0.1～50wt%, more preferably 1～40wt% usually.The size of particles of the polysuccinimide that [4-5] uses in crosslinking reaction

For the size of particles of the polysuccinimide that is in dispersed, small particle size is preferred, because can make reaction carry out easily like this.With being in size of particles (median size) under the dried forms as a kind of standard, size of particles is preferably 100 μ m or littler, more preferably 10 μ m or littler.When polysuccinimide particle such as above-mentioned suitable hour, crosslinking reaction proceeded to its inside easily, and therefore, when carrying out the hydrolysis reaction of back, noncrosslinking water-soluble portion is reduced, and can prevent the reduction of productive rate and performance thus.

In this, to reducing inhomogeneous crosslinking reaction to greatest extent, a kind of like this method of preferred employing: make polysuccinimide form more uniform dispersed really by wet lapping.This wet lapping is particularly useful to method [3-1].The detailed description of wet lapping will carry out when explaining decomposition.The linking agent that [4-6] uses in crosslinking reaction

The linking agent that the present invention is used has no particular limits, so long as with polysuccinimide in the imide ring polyfunctional compound that can react get final product.For example, can be polyfunctional compound such as polyamines and polythiol.Their object lesson can comprise polyamines, for example, and aliphatic polyamines such as hydrazine, 1, the 2-quadrol, propylene diamine, 1, the 4-butanediamine, 1, the 5-pentamethylene diamine, 1,6-hexanediamine, heptamethylene diamine, 1,8-octamethylenediamine, 1, the 9-nonamethylene diamine, decamethylene diamine, 11 methylene diamine, ten dimethylene diamines, ten tetramethylene-diamines, ten hexanediamines, 1-amino-2, two (the amino methyl)-butane of 2-, tetramino methane, diethylenetriamine and Triethylenetetramine (TETA), alicyclic ring polyamines such as norbornylene diamines, 14-diamino-cyclohexane, 1,3,5-triamino hexanaphthene, and isophorone diamine, aryl polyamines such as phenylenediamine, tolylene diamine and dimethylphenylene diamine, with Methionin and ornithine and ester thereof is the basic aminoacids of representative, and the formed compound of the one or more single-amino compounds of one or more disulfide bondings is as cystamine and derivative thereof; Aliphatic series polythiol such as 1,1,3-dimercaptopropane, 1,4-succinimide mercaptans, 1,6-ethanthiol and tetramethylolmethane; Alicyclic ring polythiol such as hexanaphthene two mercaptan; Aromatics polythiol such as xylylene two mercaptan, phenylene dimercaptan and toluene two mercaptan; And ester such as trimethylolpropane tris (sulfo-glycolate), trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (sulfo-glycolate) and tetramethylolmethane four (3-mercaptopropionic acid ester) polythiol.

Other example can comprise that with Methionin Gelucystine and ornithine and its esters and lipid are the proteinic amino acid of the formation of representative; Amino acid such as N δ-(2-amino-2-carboxy ethyl) ornithine except that constituting proteinic amino acid and its esters and lipid, N δ-(2-amino-2-carboxy ethyl) Methionin, O-(2-amino-3-hydroxypropyl) homoserine, kynurenine, α, β-diaminosuccinic acid, α, epsilon-diaminopymelic alpha acid, 2,6-diamino-7-hydroxyl nonane diacid, isolysine, 3,5-diaminocaproic acid, α, gamma-diaminobutyric alpha acid, djenkolic acid, cystathionine, cystine disulfoxide, α, ε-diamino-β-hydrogenation pimelic acid, N-(4-amino-2-hydroxyl) butyl Methionin, γ-hydroxyl ornithine, Alpha-hydroxy Methionin, L-lanthionine, Methionin base nor-leucine, rhizobiotoxin and rosin peaceful (loseanine); Amino acid derivative such as Methionin triamine; And by containing the polyamines that aminocompound molecule such as Gelucystine and cystamine are formed by connecting by disulfide linkage.

When the form of these polyamines with salt, as the hydrochloride of mineral acid salt, when vitriol or hydrobromide or organic acid salt such as tosilate or acetate exist, inorganic acid salt or organic acid salt the neutralization they after in advance the use.When the amino acid that will exist with the polyamines form during as linking agent, must the disassociation molecule inner salt, because to the structure of amino acid molecular, each carboxyl and its associating amino form with salt in molecule exist.When above-mentioned amino acid used as polyamines, polyamines used after each amino is changed into its free form, promptly neutralized each carboxyl to form carboxylate salt by add a kind of alkali in polyamines.Have no particular limits being used for neutral alkali, usually use alkali-metal oxyhydroxide such as sodium hydroxide or potassium hydroxide, alkali-metal carbonate such as yellow soda ash or salt of wormwood, alkali-metal supercarbonate such as sodium bicarbonate or saleratus, or organic amine such as triethylamine, Trimethylamine 99, trolamine, pyridine, N-methylmorpholine or picoline.

In these linking agents, those smells little and with polysuccinimide in imide have high reaction activity for preferred, that is to say preferred quadrol, propylene diamine, 1,4-butane diamines, suberane diamines, hexanediamine and cystamine.In addition, constitute proteinic amino acid such as Methionin in addition, the derivative of ornithine and Gelucystine and its esters and lipid; Amino acid such as Alpha-hydroxy Methionin except that constituting proteinic amino acid, γ-hydroxyl ornithine, and the derivative of alpha, gamma-DAB and its esters and ester; Amino acid derivative such as Methionin triamine; And cystamine also is preferred, and this is because the cross-linked poly-aspartic acid resin that generates after its degraded and/or biological degradation, is safe to Living organism and environment.Wherein, Methionin, ornithine and Gelucystine and as the derivative of salt and ester for more preferably, this is because they are not very expensive and are easy to get.They can be used alone or as a mixture.

For cross-linked poly-aspartic acid resin of the present invention,, also be preferred as linking agent with basic aminoacids from security standpoint.

Although basic aminoacids is had no particular limits, can represent by following formula (1) usually:

Wherein R represents alkylidene group, arylmethylene alkyl or arylidene.

As the alkylidene group of R, arylmethylene alkyl or arylidene can be linearity or branching or ring texture.And some carbon atoms wherein can be contained O, N, and S, P, B, the substituting group of Si etc. replaces.That is to say, alkylidene group, arylmethylene alkyl or arylidene can be contained O by one or more, N, S, P, B; the substituting group of Si etc. replaces, as ether, and ester, carbonyl, urea, thioesters, thiocarbonyl; sulfone, alkylsulfonyl, sulphonamide, secondary amine, tertiary amine, amide group, phosphonate group or phosphonic acid amide base.And, for amino, the position of substitution of R is had no particular limits.In addition, R can comprise one or more substituting groups such as alkyl, cycloalkyl, aralkyl, aryl, alkoxyalkyl, polyoxyalkylene, aryl oxidized alkene, sweet-smelling alkoxy alkyl, alkyl-thio-alkyl, polythio alkylidene group, aryl sulfo-alkylidene group, the aralkyl alkylthio, alkylamino, dialkyl amido, trialkyl amino, alkoxy carbonyl alkyl, and/or alkyl-carbonyl alkoxyl group.

Be the object lesson of R below.

-CH ₂-，-CH ₂CH ₂-，-CH ₂CH ₂CH ₂-，-CH ₂CH ₂CH ₂CH ₂-，-(CH ₂) ₅-，-(CH ₂) ₆-，-(CH ₂) ₇-，-(CH ₂) ₈-，-(CH ₂) ₉-，-(CH ₂) ₁₀-，-(CH ₂) ₁₁-，-(CH ₂) ₁₂-，-(CH ₂) ₁₃-，-(CH ₂) ₁₄-，-(CH ₂) ₁₅-，-(CH ₂) ₁₆-，-(CH ₂) ₁₇-，-(CH ₂) ₁₈-，-CH ₂CH ₂O-CH ₂CH ₂-，-(CH ₂CH ₂O) ₂CH ₂CH ₂-，-(CH ₂CH ₂O) ₃CH ₂CH ₂-，-(CH ₂CH ₂O) ₄CH ₂CH ₂-，-(CH ₂CH ₂O) ₅CH ₂CH ₂-，-(CH ₂CH ₂O) ₆-CH ₂CH ₂-，-CH ₂CH ₂CH ₂OCH ₂CH ₂CH ₂-，-(CH ₂CH ₂CH ₂O) ₂CH ₂CH ₂-CH ₂-，(CH ₂CH ₂CH ₂O) ₃CH ₂CH ₂CH ₂-，(CH ₂CH ₂CH ₂O) ₄CH ₂CH ₂CH ₂-，(CH ₂CH ₂CH ₂O) ₅CH ₂CH ₂CH ₂-，(CH ₂CH ₂CH ₂O) ₆CH ₂CH ₂CH ₂-

And, also can use amino acid dipolymer and alkaline polyamino acid such as polylysine.Wherein, Methionin and ornithine are preferred.

Although the use-pattern as the basic aminoacids of linking agent of the present invention is had no particular limits, when basic aminoacids is used for this moment, alpha-amino group and carboxyl are the zwitter-ion structure suc as formula (2) expression.In this case, alpha-amino reactive behavior reduces, to such an extent as to make the speed of response as the basic aminoacids of linking agent become very low.

The implication of R such as above-mentionedly determine wherein.

In reaction, basic aminoacids uses with the form of derivative, and as ester, thioesters or acid amides or as a feature of the present invention also can be by the carboxylate form of following formula (3) or (4) expression.By using its derivative or its carboxylate salt, alpha-amino reactive behavior is increased, and it is played a role effectively as a kind of linking agent.

Wherein the implication of R is as above-mentioned definition, and R ' represents alkyl, aralkyl or aryl, M representative-NH-,-N (R ")-, R " be alkyl, aralkyl or aryl ,-S-or-O-.

Wherein the implication of R is as above-mentioned definition, and X represents a kind of alkalimetal ion, a kind of alkaline-earth metal ions or a kind of ammonium ion.

To being used for the present invention's basic aminoacids ester, the alcohol of thioesters or acid amides, mercaptan or amine component have no particular limits, but those have small molecular weight for preferred.In addition, to basic aminoacids of the present invention in the salifiable ion of carboxylic acid shape have no particular limits.

The ionic object lesson that forms carboxylate salt can comprise alkalimetal ion such as sodium, potassium and lithium ion; Ammonium ion such as ammonium, tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA, four pentyl ammonium, tetrahexyl ammonium, ethyl trimethyl ammonium, trimethylammonium propyl ammonium, butyl trimethyl ammonium, the amyl group trimethyl ammonium, hexyl trimethyl ammonium, cyclohexyl trimethyl ammonium, benzyltrimethylammon.um, triethyl propyl ammonium, triethyl butyl ammonium, triethyl amyl group ammonium, triethyl hexyl ammonium, the ion of cyclohexyl triethyl ammonium and benzyl triethyl ammonium ammonium; Amine ion such as Trimethylamine, triethylamine, tripropylamine, tributylamine, three amylamines, three hexyl amines, trolamine, tripropanol amine, three butanolamines, three amylalcohol amine, three hexanol amine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, dicyclohexylamine, dibenzyl amine, ethylmethylamine, methyl-propyl amine, butyl methyl amine, methyl amyl amine, the methyl hexyl amine, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, the ion of amino dodecane and cetylamine.

In these ions, what those had little atom or molecular weight is preferred, and this is that the molecular weight of every monomeric unit correspondingly becomes greatly owing to the increase along with atom or molecular weight, and the water-absorbent of per unit weight correspondingly diminishes.Those have hypotoxic for preferred, and this is owing to may come in contact with people's skin or analogue.For this reason, preferably use sodium, potassium, lithium, ammonium or trolamine, and, especially preferably use sodium or potassium from the angle of economy.[4-7] amount of employed linking agent in crosslinking reaction

Amount to linking agent has no particular limits, and can determine as required, depends on the degree of crosslinking that generates cross-linked resin, and degree of crosslinking also depends on the application purpose of the cross-linked resin of generation simultaneously by the functional group's number and the molecular weight control of linking agent.The term " degree of crosslinking " that is used for this is meant at adjacent monomeric unit component number between crosslinked, or the ratio of the crosslink part of main polymer chain relatively.

Usually, how excessive linking agent causes the superhigh cross-linking degree, and consequently, when forming cross-linked poly-aspartic acid resin, its water-absorbent reduces.On the other hand, very few linking agent will cause low degree of crosslinking, and consequently, only partial cross-linked poly-aspartic acid resin is water-soluble, and can not show its water-absorbent.Thus, can determine the amount of employed linking agent like this: must obtain suitable degree of crosslinking.Usually, based on whole monomeric units of polysuccinimide, the amount of linking agent can preferred 0.1～30wt%, more preferably 1～20wt%.The catalyzer that [4-8] uses in linking agent

In crosslinking reaction, optionally can use catalyzer.As catalyzer, use basic catalyst usually.

The example of basic catalyst is an inorganic alkaline agents, for example, and alkali-metal oxyhydroxide, as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali-metal carbonate, as yellow soda ash, salt of wormwood and Quilonum Retard, alkali-metal supercarbonate, as sodium bicarbonate and saleratus, alkali-metal acetate is as sodium acetate and potassium acetate, an alkali metal salt, as sodium oxalate, and ammonium; Organic basic reagent, for example, amine, as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, triamylamine, trihexylamine, trolamine, tripropanol amine, three butanolamines, three amylalcohol amine, three hexanol amine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, dicyclohexylamine, dibenzyl amine, ethyl dimethylamine, methyl propylamine, butyl methylamine, dimethylpentylamine, tuaminoheptane, pyridine, picoline and quinoline.

The temperature of reaction of [4-9] crosslinking reaction

Temperature of reaction to crosslinking reaction has no particular limits, and can decide as the reactive behavior of linking agent and the dispersing morphology of polysuccinimide as required.Usually, can be preferred 0～200 ℃, and 10～80 ℃ for more preferably.Step after [4-10] crosslinking reaction

After crosslinking reaction is finished, can carry out following hydrolysing step, and needn't be separated in the organic solvent that uses in the crosslinking reaction.Or also can make after polysuccinimide emanates out by separating organic solvent, carry out next step hydrolysis reaction again.

Can the known method of use own carry out separating of crosslinked polysuccinimide and organic solvent.For example, can adopt filtration, decant, centrifugation etc.[5] cross-linking method of the dispersed polysuccinimide of the cross-linked poly-aspartic acid resin that improves for the preparation absorption speed

Reacting by polysuccinimide and linking agent in the inventive method for preparing crosslinked polysuccinimide, wherein, polysuccinimide is dispersed by dispersion agent, control reactions steps fully, when the imide ring hydrolysis in the crosslinked polysuccinimide, just can obtain to have the cross-linked poly-aspartic acid of high absorption speed.

The example of this method can comprise three kinds of following methods, but is not limited to this.The feeding manner of [5-1] control linking agent and dispersion agent.[5-2] will be incorporated into as the linking agent of side group on the main polymer chain, carry out the crosslinked of side group then.[5-3] then, uses surface crosslinking agent to carry out crosslinking reaction internal crosslinker and polysuccinimide reaction.

Although to how accurately using these methods to have no particular limits, the object lesson of every kind of method will be described following.

[5-1 '] linking agent and dispersion agent join in the polysuccinimide solution in good solvent simultaneously, then, form carry out under the dispersed situation crosslinked.

[5-2 '] a kind of linking agent as side group joins in the polysuccinimide solution in good solvent.Then, add dispersion agent and make reaction system form dispersed, then, add a kind of alkali and carry out crosslinking reaction.

[5-3 '] joins internal crosslinker in the polysuccinimide solution in good solvent, carries out crosslinked.Surface crosslinking agent can add dispersion agent make reaction system be dispersed after adding, also can add in the lump, thereby further carry out crosslinking reaction with dispersion agent.

There is gradient or different in the resin that these methods [5-1]～[5-3] all tends to make generation on the cross-linking density between portion and the outside within it.Particularly when this resin was used as superabsorbent polymer, the degree of crosslinking that increases resin surface can obtain good absorption speed.This is one of feature of the present invention.

Above-mentioned condition can be used in method [3] and [4] equally.Below description is different from above-mentioned condition.

How [5-1] controls the feeding manner of linking agent and dispersion agent

Charging (when comprising feed charging meter) mode by control linking agent and dispersion agent makes and can obtain a kind of good resin in this way.

In the method, linking agent and dispersion agent join among the solution of polysuccinimide in good solvent simultaneously, when reaction system is dispersed, cause crosslinking reaction.Linking agent adds with different inlets discriminably simultaneously with dispersion agent, or adds with an inlet after they are pre-mixed or dissolve.Can also be like this: linking agent can be dissolved in appropriate solvent or the water, then, adds in the same manner described above.It suitable organic solvent is had no particular limits, as long as can dissolve this linking agent basically fully.Consumption to organic solvent has no particular limits equally.

For adding linking agent and dispersion agent in the lump, the speed that they are added has no particular limits, but they dripped in 3 hours at 10 minutes usually.Too fast interpolation speed not only causes producing a large amount of heats in reaction system, nor can form good dispersed as adding at once.If but its adding surpasses 3 hours, productive rate will reduce.

In this method, optionally also can carry out using catalyzer in the process in crosslinking reaction.In this case, the timing to its interpolation has no particular limits.

How [5-2] will be incorporated on the main polymer chain and make side group crosslinked subsequently as the linking agent of side group

By polysuccinimide at first with linking agent in unique reactive group react, make it as side group, activate other reactive group then and react with crosslinked, use this method like this, just can obtain the crosslinked of polysuccinimide with side group.The linking agent that uses in this method can have the active reactive group of same reaction, but the linking agent with active two or more reactive groups of differential responses is for preferred especially.

The amino acid of enumerating in above-mentioned [4] can be used as the example of linking agent.

In each amino acid, as Methionin or ornithine, except that being used for linking agent of the present invention, in two amino one by hydrogen bond to exist with the associating form of carboxyl.On structure, it is a kind of amine of simple function group.In this form, it can not be as linking agent.By reacting with polysuccinimide, it can be used as side group and is introduced in this polymkeric substance.In the polysuccinimide that has introducing side group wherein, add a kind of alkali, consequently neutralized and other amino each carboxylic acid that forms hydrogen bond, thereby amino becomes free form, react with imide ring then.Carry out crosslinking reaction in this manner.In the present invention, above-mentioned amino acid is joined in such a manner in the solution of polysuccinimide, to such an extent as to the only amino in its molecule becomes free form.For example, so add diamino monocarboxylate such as Methionin, but when single muriate of inorganic acid salt that uses a kind of diamino monocarboxylate such as Methionin, only mineral acid is neutralized.In this manner, in the amino has been endowed free form and has been introduced in the polysuccinimide as side group.For example, when using methyl ornithine etc., if with as. this mode, crosslinking reaction will take place undesirably.Therefore, use single muriate with this form, that is to say, one of them amino is closed, and does not have activity for reaction.

The implication of term " side group " is a kind of compound with functional group as used herein, and the imide ring in itself and the polysuccinimide has reactive behavior and can open imide ring, and exists with respect to the main chain of the polysuccinimide mode with " side group ".

In this method, crosslinking reaction can be by carrying out as following three phases.

(1) linking agent is introduced into as side group.

(2) reaction system is formed dispersed, even make it when carrying out crosslinking reaction, can not form gel.

(3) add the linking agent that a kind of alkali is introduced as side group with activation, thereby cause crosslinking reaction.

The alkali that is used for activating the linking agent of introducing as side group is had no particular limits hydrogen bond between amino and the carboxyl as long as it can dissociate.Typical example is alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali-metal acetate, as sodium acetate and potassium acetate, tertiary amine such as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, triamylamine, trihexylamine, trolamine, tripropanol amine, three butanolamines, three amylalcohol amine, three hexanol amine, N-methylmorpholine, pyridine, quinoline and picoline.

For making the linking agent that is introduced into as side group complete reaction basically, must use and the alkali that is contained in the carboxyl equimolar amount in the side group.Yet, can control degree of crosslinking by the consumption of regulating alkali.That is, when the consumption of alkali during less than the carboxyl consumption in the linking agent of introducing as side group, the degree of crosslinking of generation is lower than what calculated by linking agent, to such an extent as to the linking agent part is keeping as side group always.Correspondingly, from conservative angle, above-mentioned linking agent is preferably measured and is meaned, is the amount of the alkali of required activatable crosslinking agent.

How [5-3] makes internal crosslinker and polysuccinimide reaction, carries out crosslinked with the linking agent reaction then

According to the method, polysuccinimide at first reacts with internal crosslinker, carries out crosslinking reaction with surface crosslinking agent then.Compare with [5-2] with method [5-1], produce different or gradient on the cross-linking density between the easier inside at each resin particle of this method [5-3] and the outside.

But this method is the principle of using method [5-1] and [5-2] also.

The implication that is used for this term " internal crosslinker " is a kind of before adding dispersion agent, the linking agent that reacts with polysuccinimide in homogeneous system.In addition, the implication of term " surface crosslinking agent " is a kind of after adding dispersion agent, with the linking agent of the polysuccinimide reaction that is in dispersed.

As illustrated in the method [5-2], when a kind of its neutralized by alkali in advance and contain the polyamines of (polyamino) polycarboxylic acid of at least two amino (as contain the polyamines of at least one carboxyl in a molecule) and/or a kind of routine or polythiol as linking agent, the same with common linking agent and cause crosslinking reaction, and when using a kind of amino on it as (polyamino) polycarboxylic acid of free form, it at first is introduced into as side group.Therefore, this method [5-3] will be described following, wherein, which in this two type of crosslinking agent as internal crosslinker, it will be divided into two parts according to.[5-3-1] a kind of its neutralized by alkali in advance and contained the polyamines of (polyamino) polycarboxylic acid of at least two amino (as contain the polyamines of at least one carboxyl in a molecule) and/or a kind of routine or polythiol as internal crosslinker

In this method, for example, crosslinking reaction can be carried out through following three phases.

(1) can not the induce reaction internal crosslinker and the polysuccinimide of system gel of a kind of its consumption reacts.

(2) adding dispersion agent makes reaction system be dispersed.

(3) add surface crosslinking agent further to carry out crosslinking reaction.

Stage (2) and (3) can be carried out simultaneously.Be that the form that surface crosslinking agent can join in the reaction system with dispersion agent or surface crosslinking agent can be dissolved in the dispersion agent adds.As the surface crosslinking agent of present method, can use the above-mentioned polyfunctional compound that has reactive behavior with imide ring, as polyamines and polythiol.

In this case, the consumption (whole consumptions of internal crosslinker and/or surface crosslinking agent) of linking agent is had no particular limits, can select suitable consumption according to required degree of crosslinking.Term " degree of crosslinking " implication that is used for this is meant the ratio of the crosslink part of relative main polymer chain.Usually, a large amount of excessive linking agents cause the superhigh cross-linking degree, and consequently, when forming superabsorbent polymer, its water-absorbent reduces.On the other hand, very few linking agent will cause low degree of crosslinking, and consequently, only partial cross-linked poly aspartic acid is water-soluble, and can not show its water-absorbent.Thus, the consumption of linking agent (whole consumptions of internal crosslinker and/or surface crosslinking agent), based on the whole monomeric unit numbers on the polysuccinimide main chain, usually, the amount of linking agent can be adjusted into 0.1～30mol%, the consumption of the system agglomerative internal crosslinker that do not induce reaction in the above-mentioned steps (1), based on the whole monomeric unit numbers on the polysuccinimide main chain, be generally 0.01～3mol%, its consumption also depends on the kind of linking agent, the molecular weight of temperature of reaction and polysuccinimide.That is to say, in homogeneous system, crosslinking reaction proceeds to its degree of crosslinking and is about 0.01～3%, adding dispersion agent after this makes reaction system be dispersed, or the consumption of the surface crosslinking agent that can add in the lump with dispersion agent, based on the whole degree of crosslinking that comprise the degree of crosslinking that obtains by internal crosslinker, be enough degree of crosslinking of acquisition 0.1～30%, then, continue further crosslinking reaction.

[5-3-2] only uses wherein, and an amino is that free form (polyamino) polycarboxylic acid is as internal crosslinker

In this method, for example, crosslinked can carrying out by following four-stage.

(1) introducing is as the internal crosslinker of side group.

(2) make reaction system be dispersion state,, also can avoid the gelation of reaction system potential even when crosslinking reaction is carried out.

(3) add the internal crosslinker that a kind of alkali is introduced as side group with activation, thereby crosslinking reaction is carried out.

(4) it is surface-crosslinked to carry out to add surface crosslinking agent then.

As surface crosslinking agent, can use the above-mentioned polyfunctional compound that has reactive behavior with imide ring, as polyamines or polythiol.

In this case, the consumption to linking agent has no particular limits equally.Yet, regulate the consumption of linking agent usually, so that,, be 0.1～30mol% based on the whole monomeric unit numbers on the polysuccinimide main chain as the total amount of the internal crosslinker of side group introducing with the surface crosslinking agent of adding after disperseing.Although have no particular limits to the surface crosslinking agent of adding after disperseing and as the molar ratio between the internal crosslinker of side group introducing, but the ratio of the surface crosslinking agent that adds after disperseing is too high, in other words, surface crosslinking agent with high per-cent will finally obtain the superabsorbent polymer of high absorption speed, otherwise it has low water absorbable.Therefore, based on its application purpose, can select suitable molar ratio.

About the kind and the consumption of employed alkali and use the control of its consumption to degree of crosslinking, in above-mentioned [5-3-1], describe accordingly, be suitable for this too.

Under the situation of above-mentioned [5-3-2], to introducing internal crosslinker, undertaken crosslinkedly by adding alkali as side group, and carry out surface-crosslinked temperature and have no particular limits by adding surface crosslinking agent.Yet the typical temperature of these reactions is-10～200 ℃, and preferred 10～80 ℃, certainly, they can also depend on the reactive behavior of linking agent, have catalyzer, the molecular weight of polysuccinimide etc.[6] cross-linking method of polysuccinimide under the non-dispersive state

In the above description, described by making the polysuccinimide and the linking agent that are dispersed by dispersion agent react the method for preparing crosslinked polysuccinimide.According to the method described above, by simple technology, can high yield obtain crosslinked polysuccinimide.

Yet, it should be noted that, the present invention comprises that not only feature is the cross-linking method that is in the polysuccinimide of dispersed, and comprise a kind of like this method, promptly in the method, the polysuccinimide of solution form is cross-linked into gel, and then, so the polysuccinimide gel that obtains decomposes.As will be described later, the present invention also comprises and is characterised in that the method for hydrolysis of regulating the resin swelling degree, and comprises the method that makes water and/or can wash and deposit the cross-linked poly-aspartic acid resin gel with the miscible organic solvent of water that is characterised in that.

From practical angle, when these methods and the cross-linking method that is characterised in that the polysuccinimide that is in dispersed, or be cross-linked into gel with the polysuccinimide of solution form, the method that the polysuccinimide gel that will so obtain then decomposes is mixed when using, and these methods seem more practical.The cross-linking method that is in the polysuccinimide of non-dispersive attitude will be described below.In addition, the implication of term " non-dispersive attitude " is a kind of uniform polysuccinimide solution as used herein, or a kind ofly is different from very much solution but near the form of solution, in this kind form, dispersion agent not only is in the dissolving form, and is in dispersing morphology.While also comprises the form that a kind of part polysuccinimide does not have dissolving and deposition to come out.

In this case, polysuccinimide and linking agent react in good solvent, that is to say, so-called good solvent is the organic solvent that can dissolve polysuccinimide.Its example is N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), and tetramethylene sulfone.Wherein, N, dinethylformamide, N,N-dimethylacetamide is for more preferably, and this is because they have high resolution to polysuccinimide.These solvents can use or mix use separately.

In addition, from slowing down the angle of crosslinking reaction, also can add a kind of poor solvent, it can not dissolve or only can the slightly soluble polysuccinimide.As such poor solvent, can use with above-mentioned and enumerate identical poor solvent.

When crosslinking reaction was carried out, the crosslinking reaction system was constantly by gelling.The carrying out of hydrolysis reaction can be before the whole gellings of reaction system or after the whole gellings of reaction system.The agglomerative degree depends on the concentration of reaction conditions such as polymkeric substance, the consumption of linking agent, the ratio (if any) that degree of crosslinking and poor solvent are shared.Such as high polymers concentration, a large amount of linking agents, under the condition of the poor solvent of high-crosslinking-degree or low ratio, the gel of generation is hard.And under opposite condition, this gel is soft.In this case, can select the gel that will form according to the application purpose that gets cross-linked poly-aspartic acid resin through hydrolysis.For obtaining to have the resin of high-gel strength, for example, only need to increase degree of crosslinking.Under soft gel situation,, can make its decomposition by in poor solvent or water, disperseing this gel as disclosed among the JP7-224163.Under hard gel situation, yet this method can not fully be decomposed this gel at short notice, thereby makes hydrolysis reaction carry out difficulty.In this case, a kind of method that makes crosslinked polysuccinimide gel carry out very effectively decomposing is one of feature of the present invention.That is, after crosslinking reaction, become owing to absorb organic solvent the swollen gel a kind of as the crosslinked polysuccinimide of reaction product.After making its decomposition, preferably use this gel.In this case, this gel can take out after crosslinking reaction, be fed to then in a kind of wet lapping machine, or crosslinking reaction itself can carry out in the wet lapping machine, and same gelation is also carried out in this machine.

The wet lapping of the crosslinked polysuccinimide of the present invention, for non-soft gel, even if soft, be that effectively therefore, hydrolysis can be carried out at short notice.[7] decompose

Especially for being in the crosslinked polysuccinimide that non-dispersive attitude polysuccinimide gets, advantageous applications decomposition reaction by crosslinked.In addition, make dispersed more even by the crosslinking reaction under decomposing state, this also is preferred.That is to say, when the polysuccinimide that forms, is in dispersed by dispersion agent when aforesaid use carries out crosslinking reaction, carry out wet lapping.Two kinds of situations will be described below together.

Term " decomposition " is interpreted as comprising a kind of scheme as used herein, and in this scheme, reactive material (gel etc.) is decomposed, and another kind of scheme, and in this scheme, reactive material is ground in water and/or organic solvent.In addition, this term also comprises " wet lapping " on the ordinary meaning.

As a kind of operation splitting, be preferably in water and/or organic solvent and decompose, or decompose the material that will react, then,, add a kind of transfer solvent (water and/organic solvent) to give its flowability from shifting and similar angle.The solvent that [7-1] uses in decomposition

The solvent that uses in decomposition is had no particular limits.The solvent that is generally used for this purpose all is available.Its concrete example can comprise water, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), and tetramethylene sulfone, alcohol is as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, octanol, 2-methyl cellosolve and cellosolvo; Glycol such as ethylene glycol, glycol ether, triglycol, propylene glycol and dipropylene glycol; Gylcol ether such as ethylene glycol monomethyl ether and ethylene glycol ethyl ether; Ketone such as acetone, methylethylketone and methyl iso-butyl ketone (MIBK); Cyclic ethers such as tetrahydrofuran (THF) are with diox; Sherwood oil; Pentane; Hexane; Heptane; Octane; Hexanaphthene; Benzene; Toluene; Ethylbenzene; Dimethylbenzene; Naphthalane; Phenyl ether; Methyl-phenoxide; And cresols.These solvents can be used alone or as a mixture.The shredder that [7-2] uses in decomposition

Employed shredder is had no particular limits, as long as it can decompose a kind of solid substantially, a kind of gel shape material, a kind of solid or a kind of gel shape material in liquid in liquid gets final product.As concrete example, those types with tool edge type stirring rake or common stirring rake and rotation at full speed are for preferred.For improving decomposing efficiency, the shredder of being furnished with traverse baffle also is preferred.In addition, have simultaneously and decompose and the shredder of forwarding function also is preferred.Shape to stirring rake has no particular limits, and stirring rake can be a screw form, or ribbon shape or the very light wire stirring rake of handling big load.

Its exemplary can comprise the pipeline homo-mixer, uniform mixing pipeline machine, goratol pump, splitter, mixing tank, feeding machine, homogenizer, meat mincer, flour stranding machine, coffee machine, juice mixing tank, vortex mixer, drum tumbler etc.

Reality the stirring rake that has tool edge type or the rotating speed (rpm, rotations per minute) of common stirring rake had no particular limits, as long as can be decomposed.Normally, in the scope that the temperature of grinding system can not raise because of heat of friction, is preferred at a high speed.When this resin is applied on disposable diaper or agricultural or the gardening with the macroparticle form, 10～10,000rpm is preferred, wherein 100～5,000rpm is for more preferably.When this resin during as the thickening material of polymkeric substance or additive, 100～100,000rpm be preferably, wherein 1,000～50,000rpm is for more preferably.

Decomposition can one step or a few stage by stage step carry out.For the size of particles (median size) of polysuccinimide gel, through decomposition and size of particles, or in the crosslinking reaction process, be in the size of particles (median size) of polysuccinimide gel under the dispersed, have no particular limits.Concerning crosslinked polysuccinimide, preferred little size of particles, this is because reaction can be carried out under more uniform dispersed.Size of particles is generally 0.00001～1mm, and wherein 0.0001～0.1mm is for more preferably.When common size of particles when the dispersive product is too big, its speed of response will reduce.In addition, the application purpose or the others of the cross-linked poly-aspartic acid resin of generation are depended in the variation of the size of particles of crosslinked polysuccinimide.When joining crosslinked polysuccinimide in other resin or the analogue, preferred undersized crosslinked polysuccinimide resin, this is because the primary particle size decreases of the cross-linked poly-aspartic acid resin that is generated.Size of particles is generally 0.00001～1mm, and wherein 0.0001～0.1mm is for more preferably.When common size of particles when the dispersive product is too big, its speed of response will reduce.When this cross-linked poly-aspartic acid resin was applied on disposable diaper or agricultural or the gardening, concerning cross-linked poly-aspartic acid resin, preferred big relatively size of particles was so that the crosslinked polysuccinimide in the decomposition course can preferably have the macroparticle size.The reaction conditions of crosslinking reaction is depended in the variation of its size of particles, and can not specify in large quantity.However, 0.01～20mm is preferred, and wherein 0.1～2mm more preferably.

When will be by the crosslinked polysuccinimide that is in the non-dispersive attitude crosslinked polysuccinimide gel so decompose the time, make the gel of decomposition carry out the hydrolysis reaction of imide ring then.In the hydrolysis reaction step, make water usually as base stock.When decomposition reaction water and/or can with the miscible organic solvent of water in when carrying out, and then hydrolysing step can carry out, and needn't isolate the gel of decomposition.

In addition,, also can before material decomposition, add a kind of salt (organic salt and/or inorganic salt), decompose then, then make the decomposition of the mixture of generation directly enter into following hydrolysing step hydrolysis reaction.And, the alkaline aqueous solution of hydrolysis reaction can be added with decomposing the same time, so that decomposition and hydrolysis reaction carry out in the lump.

When in organic solvent, obtaining a kind of solids slurry by decomposing, then this solid is separated from organic solvent, from reclaiming the angle of solid or solvent, separablely go out this solid.As preferred separation method, can comprise conventional chemical separation method such as decant or centrifugation.Like this solid that obtains, after drying or directly the form with wet cake enters into next hydrolysing step.In other words, before hydrolysing step, can remove organic solvent, or can directly be hydrolyzed step and needn't remove organic solvent.[8] application purpose of crosslinked polysuccinimide

As mentioned above, can be by simple technology, the crosslinked polysuccinimide of produced in high yields, in the method, the polysuccinimide and the linking agent that are formed dispersed by dispersion agent react.In addition, also can a kind of simple method prepare crosslinked polysuccinimide, in this method, the gel of crosslinked polysuccinimide be decomposed.In the crosslinking reaction of method, the imide ring and the linking agent of some polysuccinimides react in front, thereby its ring is opened.Residual imide ring carries out alkaline hydrolysis on the crosslinked polysuccinimide that generates, and so just can obtain good cross-linked poly-aspartic acid resin.That is, this crosslinked polysuccinimide is very useful as a kind of intermediate in the preparation cross-linked poly-aspartic acid resin.

Yet, it should be noted that the application purpose of crosslinked polysuccinimide is not limited only to as a kind of intermediate.As a kind of resin material, crosslinked polysuccinimide itself can be used for various application purposes.Its use-pattern also can be identical with " use-pattern of cross-linked poly-aspartic acid resin " that the back will be mentioned.Its use shape also can be identical with " shape of cross-linked poly-aspartic acid resin " that the back will be mentioned.[9] regulate the hydrolysis of imide ring of the crosslinked polysuccinimide of swelling capacity in advance

Prepare in the method for cross-linked poly-aspartic acid resin in the present invention, in the imide ring that makes crosslinked polysuccinimide was hydrolyzed reaction process, the resin swelling degree in the reaction system was controlled in 3～100 times.By this control, can promptly be hydrolyzed, thereby can obtain to improve absorptive cross-linked poly-aspartic acid resin.The implication that is used for this term " molten length " is that when resin was hydrolyzed reaction, the resin in the reaction system absorbed water, organic solvent, salt, the degree of absorption of oligopolymer etc. (quantity).At this moment, this resin forms solvent swelling state owing to absorb them.To stir be difficult to resin under solvent swelling state, if but have excess liq, stirring is fine.Can in the presence of excessive water, carry out such hydrolysis reaction.Therefore, in the specified scope of the present invention, under the situation that keeps the resin swelling degree, stirring can successfully be carried out.The amount of excess liq depends on the efficient of stirrer.When the stirrer that has high torque (HT) during with the operation of high revolution, excess liq can be on a small quantity, if but stirrer can not so move, then this excessive liquid must be a large amount of.

In addition, also may prevent this situation: because further hydrolysis, gel shape resin absorbs more water and becomes solid form.And, also can avoid such a case: because the curing and the sedimentary cohesion of gel shape resin are stirred and become very difficult.This just may increase the concentration of resin in the reaction mixture, thereby increases its volumetric efficiency.

The span of control of swelling capacity is preferred at 3～100 times, and wherein 5～20 times for more preferably.

In the present invention, need in the whole process of reaction, not carry out the hydrolysis reaction of imide ring.In some stage, swelling capacity can be temporarily in this scope.Can allow so temporarily departing from.For example, the swelling capacity in the reaction starting stage that hydrolysis reaction does not also carry out fully may be substantially of zero (0), therefore can depart from above-mentioned scope.In the time need not specializing concrete swelling capacity in advance and prepare resin, swelling capacity can depart from above-mentioned scope significantly.Preparation method of the present invention can easily proofread and correct the swelling capacity of resin, even it departs from above-mentioned scope significantly.The present invention can make the reaction that promptly is hydrolyzed of the imide ring in the crosslinked polysuccinimide, and has splendid operability.On these angles, even if it is as with the substep form but not the ordinary method of this hydrolysis reaction, this method is also contained among the present invention.

Control swelling capacity four kinds of methods below the object lesson of 3～100 times of methods can comprise.

[9-1] contain can with the reaction that is hydrolyzed in the miscible organic solvent solution of water.

[9-2] reaction that in the aqueous solution that contains inorganic salt and/or organic salt, is hydrolyzed.

[9-3] reaction that in 40～100 ℃ solvent, is hydrolyzed.

[9-4] optionally, in conjunction with at least two kinds of methods among [9-1]～[9-3], reaction is hydrolyzed.

To be described method [9-1]～[9-4] following.

[9-1] contain can with the miscible aqueous solutions of organic solvent of water in be hydrolyzed the reaction method

In this method, the control of gel shape resin swelling in the reaction system, be by suitably determine aqueous solution Zhong Shui with can finish with ratio and other condition (kind of organic solvent etc.) of the miscible organic solvent of water.

To having no particular limits, as long as it is a kind of organic solvent that can be miscible with water with the miscible organic solvent of water.Its concrete example can comprise alcohol as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, amylalcohol, hexanol, enanthol, octanol, 2-methyl cellosolve and cellosolvo; Glycol such as ethylene glycol, glycol ether, triglycol, propylene glycol and propylene glycol; Ketone such as acetone, methylethylketone and methyl iso-butyl ketone (MIBK); Cyclic ethers such as tetrahydrofuran (THF) are with diox; N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), and tetramethylene sulfone.Methyl alcohol wherein, ethanol, propyl alcohol, Virahol and butanols are for preferred especially, and this is that after drying, solvent remains in the resin hardly because the resin that generates can be easily dry.

In hydrolytic process, can be particularly important with the miscible organic solvent of water and the amount and their ratio of water.Their suitable values depend on can with the polarity of the miscible organic solvent of water, and be decided by water and can with the polarity of the mixed solvent of the miscible organic solvent of water.For example, when their ratio is set at 100% water, can obtain maximum absorptive cross-linked poly-aspartic acid resin.And when the ratio of organic solvent becomes big, the water-absorbent of resin will diminish.Surpass to a certain degree when the ratio of organic solvent is increased to, the resin that is generated can not show water-absorbent basically.

Discovery according to the inventor, hydrolysis reaction in the water for preparing cross-linked poly-aspartic acid resin by the imide ring hydrolysis in the crosslinked polysuccinimide, consequently, because the cause of suction, the resin in the reaction system carries out swelling and carries out gelation basically.Thereby, be difficult to the stirring of reaction system.Hydrolysing agent thereby can not be disperseed is to such an extent as to reaction can not fully be carried out.This problem that causes is that the cross-linked poly-aspartic acid resin that is generated can not provide high-hydroscopicity.And, hydrolysis reaction in the mixed solvent (this mixed solvent contains the organic solvent of vast scale) of organic solvent or water and organic solvent, to make the resin in the reaction system only carry out hydrolysis reaction on particle surface, this just greatly reduces the speed of response of hydrolysis.Simultaneously also caused such problem: the cross-linked poly-aspartic acid resin of generation can not provide high-hydroscopicity.

When making water and can be with the mixed solvent of the miscible organic solvent of water the time, the swelling capacity of the cross-linked poly-aspartic acid resin of generation by as above-mentioned their ratio decision.In the method for the invention, during hydrolysis reaction, optionally regulate their ratio, make that the swelling capacity of resin is controlled at 3～100 times in the reaction system.Under the situation of resin swelling, the migration of liquid in the resin such as water or organic solvent will take a long time.For by absorbing or discharge liquid to reach the equilibrated resin, be necessary time of relaxation.Thereby, for obtaining the resin of desired swelling capacity, after the ratio of control water and organic solvent,, also need for some time to obtaining desired swelling capacity.

And, reaction system Zhong Shui with can with the ratio of water miscibles organic solvent, can optionally change, its method is, when needs make after initial action water and can with imide ring in the crosslinked polysuccinimide in the mixed solvent of water miscibles organic solvent further during hydrolysis, with fresh water or can join in the reaction mixture with the miscible organic solvent of water.

For example, when the water-absorbent of the cross-linked poly-aspartic acid resin that will prepare is not limited to special value, the hydrolysis reaction of imide ring can water or water and can with the mixed solvent of water miscibles organic solvent in cause, mixed solvent contains the organic solvent with respect to the water height ratio.When the gelation owing to resin makes resin carry out thickening, can be with can the joining in the reaction mixture of requirement with the miscible organic solvent of water, thereby can prevent thickening.

For example, also can with the miscible organic solvent of water in or water and can with the mixed solvent of water miscibles organic solvent in, cause the hydrolysis reaction of imide ring, this mixed solvent contains the organic solvent with respect to the water height ratio, then, for preventing sedimentary cohesion, the water of needs is joined in the reaction mixture.That is to say that method of the present invention is highly effective, it not only makes the resin that will prepare have preassigned water-absorbent, and makes the resin that will prepare have not preassigned water-absorbent.

Water with can with the mixed solvent of water miscibles organic solvent in, the ratio of water can be preferably 5wt% or higher, wherein 20～80wt% is for more preferably.

And, can be with isolating crosslinked polysuccinimide, be contained in wet cheese formula wherein always or join following hydrolysing step with solvent with the form that drying removes solvent.The method that [9-2] is hydrolyzed in the aqueous solution that contains inorganic salt and/or organic salt and reacts

In this method, hydrolysis reaction carries out under the situation that has inorganic salt and/or organic salt.Be the osmotic pressure of conditioned reaction system, suitably determine the concentration and the kind of inorganic salt and/or organic salt, the swelling capacity of gel shape resin is controlled.

Organic salt and inorganic salt are had no particular limits, the conventional salt such as the neutral salt of wide region, basic salt and acid-salt all can use.When using polyvalent metal salt, the salt that preferred concentration is lower, this is that the cross-linked poly-aspartic acid resin that causes so obtaining has high-crosslinking-degree because polyvalent metal salt can cause the ionomer of the carboxylic acid that is formed by the imide hydrolysis.

Can use by adding the solution that inorganic salt or organic salt form, maybe can use a kind of salt that neutralization forms in water.And if a kind of salt obtains in the crosslinking reaction in front, this salt can directly use so.

The example of available salt can comprise metal-salt, organic alkali salt, and the oxide compound of mineral acid and analogue thereof, these acid are example hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, sulfuric acid, sulfurous acid, pyrosulfuric acid, amidosulphuric acid, thiosulfuric acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, ortho-phosphoric acid, metaphosphoric acid, diphosphanetetroic acid, tetra-sodium, Hypophosporous Acid, 50, phosphonic acids, carbonic acid, percarbonic acid, boric acid, ortho-boric acid, metaboric acid, chloric acid, perchloric acid, hypochlorous acid, bromic acid, hyperbromic acid, hypobromous acid, acid iodide, Periodic acid, hypoiodous acid, silicic acid, orthosilicic acid, silicic acid (H ₂SiO ₃), aluminic acid, telluric acid, isocyanic acid, thiocyanic acid, mangaic acid, permanganic acid, Periodic acid, chromic acid, dichromic acid, metantimonic acid, metavanadic acid and molybdic acid; Organic acid such as organic phospho acid, organic sulfonic acid, organic carboxyl acid, oxalic acid and organic phenol.

Wherein, metal-salt and hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, sulfuric acid, sulfurous acid, pyrosulfuric acid, amidosulphuric acid, thiosulfuric acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, ortho-phosphoric acid, metaphosphoric acid, diphosphanetetroic acid, tetra-sodium, Hypophosporous Acid, 50, phosphonic acids, carbonic acid, boric acid, ortho-boric acid, metaboric acid, silicic acid, orthosilicic acid, silicic acid (H ₂SiO ₃), oxalic acid, organic phospho acid, organic sulfonic acid, organic alkali salt of organic carboxyl acid are preferred, because they have hypotoxicity, do not have oxidation-reduction quality, and expense are low.Particularly preferred is metal-salt and various sour example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, organic alkali salt of organic phospho acid organic sulfonic acid and organic carboxyl acid.

The metal example that constitutes metal-salt can comprise lithium, sodium, potassium, beryllium, magnesium, aluminium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, pincers, germanium, rubidium, strontium, ytterbium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, tellurium, caesium, barium, cerium, gold, mercury, thallium and lead.Lithium wherein, sodium and potassium are preferred, because they have hypotoxicity, expense is low and can high dissolution in water.

In addition, the example of organic salt can comprise ammonium salt such as ammonium, tetramethylammonium, Tetrylammonium, tetrapropylammonium, tetrabutylammonium, 4 penta ammoniums, four own ammoniums, ethyl trimethyl ammonium, trimethylammonium propyl ammonium, butyl trimethyl ammonium, the amyl group trimethyl ammonium, hexyl trimethyl ammonium, cyclohexyl trimethyl ammonium, benzyltrimethylammon.um, triethyl propyl ammonium, triethyl butyl ammonium, triethyl amyl group ammonium, triethyl hexyl ammonium, cyclohexyl triethyl ammonium and benzyl triethyl ammonium ammonium; Amine salt such as Trimethylamine, triethylamine, tripropylamine, tributylamine, three amylamines, three hexyl amines, trolamine, tripropanol amine, three butanolamines, three amylalcohol amine, three hexanol amine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, dicyclohexylamine, dibenzyl amine, ethylmethylamine, methyl-propyl amine, butyl methyl amine, methyl amyl amine, the methyl hexyl amine, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, amino dodecane and cetylamine.

Wherein, the solvability from water, smell, the angle of safety and expense considers, more preferably ammonium salt such as tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA, ethyl trimethyl ammonium, benzyltrimethylammon.um and benzyl triethyl ammonium ammonium; Amine salt such as Trimethylamine, triethylamine, tripropylamine, tributylamine and trolamine.

Other object lesson comprises muriate such as sodium-chlor, Repone K, lithium chloride, ammonium chloride, calcium chloride, magnesium chloride, beryllium chloride, aluminum chloride, titanium tetrachloride, vanadium chloride, chromium chloride, Manganous chloride tetrahydrate, iron(ic) chloride, cobalt chloride, nickelous chloride, cupric chloride, zinc chloride, strontium chloride, Ytterbium trichloride, zirconium chloride, molybdenum chloride, ruthenium chloride, rhodium chloride, Palladous chloride, silver chloride, Cadmium chloride fine powder, tin chloride, tellurium chloride, cesium chloride, bariumchloride, Cerium II Chloride, lead chloride, tetramethylammonium chloride, tetraethylammonium chloride, TBAC tetrabutylammonium chloride and hydrochlorinate trolamine, Sodium Bromide, Potassium Bromide, lithiumbromide, brometo de amonio, tetramethylammonium bromide, tetraethyl-ammonium bromide, bromination tetrabutylammonium, hydrogen bromination trolamine, sodium iodide, potassiumiodide, lithium iodide, ammonium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, hydrogen iodate trolamine, sodium sulfate, vitriolate of tartar, Lithium Sulphate, ammonium sulfate, sulfation tetramethylammonium, sulfation Tetrylammonium, the sulfation tetrabutylammonium, sulfation trolamine, SODIUMNITRATE, saltpetre, lithium nitrate, ammonium nitrate, the nitrification tetramethylammonium, nitrification Tetrylammonium, nitrification tetrabutylammonium, the nitrification trolamine, sodium phosphate, potassiumphosphate, Trilithium phosphate, ammonium phosphate, yellow soda ash, salt of wormwood, Quilonum Retard, volatile salt, the carbonic acid tetramethylammonium, carbonic acid Tetrylammonium, carbonic acid tetrabutylammonium, the carbonic acid trolamine, Sodium Tetraborate, potassium borate, lithium tetraborate, ammonium borate, benzene sulfonic acid sodium salt, Phenylsulfonic acid potassium, Phenylsulfonic acid lithium, ammonium benzene sulfonate, the Phenylsulfonic acid tetramethylammonium, Phenylsulfonic acid Tetrylammonium, Phenylsulfonic acid tetrabutylammonium, the Phenylsulfonic acid trolamine, paratoluenesulfonic acid sodium salt, tosic acid potassium, the tosic acid lithium, paratoluenesulfonic acid ammonium salt, tosic acid tetramethylammonium, tetraethyl ammmonium p toluene sulfonate, tosic acid tetrabutylammonium, tosic acid trolamine, Sodium Benzoate, potassium benzoate, lithium benzoate, ammonium benzoate, phenylformic acid tetramethylammonium, phenylformic acid Tetrylammonium, the phenylformic acid tetrabutylammonium, phenylformic acid trolamine, sodium oxalate, potassium oxalate, lithium oxalate, ammonium oxalate, the oxalic acid tetramethylammonium, oxalic acid Tetrylammonium, oxalic acid tetrabutylammonium, the oxalic acid trolamine, sodium acetate, potassium acetate, lithium acetate, ammonium acetate, acetate tetramethylammonium, the acetate Tetrylammonium, acetate tetrabutylammonium, acetate trolamine, Sodium Propionate, potassium propionate, propionic acid lithium, propionic acid ammonium, the propionic acid tetramethylammonium, the propionic acid Tetrylammonium, propionic acid tetrabutylammonium, propionic acid trolamine.

Wherein, be preferably sodium-chlor, Repone K, lithium chloride, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, TBAC tetrabutylammonium chloride and hydrochlorinate trolamine, Sodium Bromide, Potassium Bromide, lithiumbromide, brometo de amonio, tetramethylammonium bromide, tetraethyl-ammonium bromide, bromination tetrabutylammonium, hydrogen bromination trolamine, sodium iodide, potassiumiodide, lithium iodide, ammonium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, hydrogen iodate trolamine, sodium sulfate, vitriolate of tartar, Lithium Sulphate, ammonium sulfate, sulfation tetramethylammonium, sulfation Tetrylammonium, the sulfation tetrabutylammonium, sulfation trolamine, SODIUMNITRATE, saltpetre, lithium nitrate, ammonium nitrate, the nitrification tetramethylammonium, nitrification Tetrylammonium, nitrification tetrabutylammonium, the nitrification trolamine, sodium phosphate, potassiumphosphate, Trilithium phosphate, ammonium phosphate, yellow soda ash, salt of wormwood, Quilonum Retard, volatile salt, the carbonic acid tetramethylammonium, carbonic acid Tetrylammonium, carbonic acid tetrabutylammonium, the carbonic acid trolamine, Sodium Tetraborate, potassium borate, lithium tetraborate, ammonium borate, benzene sulfonic acid sodium salt, Phenylsulfonic acid potassium, Phenylsulfonic acid lithium, ammonium benzene sulfonate, the Phenylsulfonic acid tetramethylammonium, Phenylsulfonic acid Tetrylammonium, Phenylsulfonic acid tetrabutylammonium, the Phenylsulfonic acid trolamine, paratoluenesulfonic acid sodium salt, tosic acid potassium, the tosic acid lithium, paratoluenesulfonic acid ammonium salt, tosic acid tetramethylammonium, tetraethyl ammmonium p toluene sulfonate, tosic acid tetrabutylammonium, tosic acid trolamine, Sodium Benzoate, potassium benzoate, lithium benzoate, ammonium benzoate, phenylformic acid tetramethylammonium, phenylformic acid Tetrylammonium, the phenylformic acid tetrabutylammonium, phenylformic acid trolamine, sodium oxalate, potassium oxalate, lithium oxalate, ammonium oxalate, sodium acetate, potassium acetate, lithium acetate, ammonium acetate, acetate tetramethylammonium, acetate Tetrylammonium, the acetate tetrabutylammonium, acetate trolamine, Sodium Propionate and potassium propionate.More preferably.Sodium-chlor, Repone K, ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, TBAC tetrabutylammonium chloride and hydrochlorinate trolamine, sodium sulfate, vitriolate of tartar, ammonium sulfate, sulfation tetramethylammonium, sulfation Tetrylammonium, sulfation tetrabutylammonium, the sulfation trolamine, sodium phosphate, potassiumphosphate, ammonium phosphate, yellow soda ash, salt of wormwood, volatile salt, Sodium Tetraborate, potassium borate, ammonium borate, benzene sulfonic acid sodium salt, Phenylsulfonic acid potassium, ammonium benzene sulfonate, Phenylsulfonic acid tetramethylammonium, Phenylsulfonic acid Tetrylammonium, Phenylsulfonic acid tetrabutylammonium, the Phenylsulfonic acid trolamine, paratoluenesulfonic acid sodium salt, tosic acid potassium, paratoluenesulfonic acid ammonium salt, the tosic acid tetramethylammonium, tetraethyl ammmonium p toluene sulfonate, tosic acid tetrabutylammonium, tosic acid trolamine, Sodium Benzoate, potassium benzoate, ammonium benzoate, sodium oxalate, potassium oxalate, ammonium oxalate, sodium acetate, potassium acetate, ammonium acetate, Sodium Propionate and potassium propionate.

The above-mentioned various salt of enumerating can be used alone or as a mixture.In some cases, they also can mix use with inorganic salt and organic salt.

In this method, can add this salt in the starting stage of reaction, or can during reaction optionally add.The salt that adds can be controlled the swelling capacity that generates gel.

The concentration of this salt in reaction mixture can be preferably 0.01～20wt%, and wherein 0.1～5wt% is for more preferably.Suitably the salt of high density can embody the effect of salt, and suitably the salt of lower concentration can prevent that the mixture of salt from entering into resin inside.

In this method, organic solvent can with the aqueous solution of inorganic salt and/or organic salt.Organic solvent comprise can with the miscible organic solvent of water and with the immiscible two kinds of organic solvents of water, two kinds all can be used.

Can with the miscible organic solvent object lesson of water can with in aforesaid method [9-1], enumerate can be identical with the miscible organic solvent of water.In addition, the object lesson with the immiscible organic solvent of water can comprise sherwood oil, pentane, hexane, heptane, octane, hexanaphthene, benzene, toluene, ethylbenzene, dimethylbenzene, naphthalane and biphenyl ether.Organic solvent such as methyl alcohol that more preferably can be miscible wherein with water, ethanol, propyl alcohol, Virahol and butanols, this be because by hydrolysis reaction cross-linked poly-aspartic acid resin can carry out drying at an easy rate, and in dried resin residual solvent hardly.

When making the mixed solvent of water and organic solvent, the ratio of water can be preferably 5wt% or higher in the mixed solvent, and wherein 20～80wt% is for more preferably.The method that [9-3] is hydrolyzed in 40～100 ℃ solvent and reacts

In this method, by using the cross-linked poly-aspartic acid resin at high temperature characteristic of its water-absorbent reduction, the suitably temperature of conditioned reaction mixture.Thereby the swelling capacity of gel shape resin in the control reaction system.

The solvent that uses in this method can be the water or the aqueous solution that contains organic solvent.Organic solvent comprise can with the miscible organic solvent of water and with the immiscible two kinds of organic solvents of water, two kinds all can be used.As can with the miscible organic solvent of water and with the object lesson of the immiscible organic solvent of water, can comprise those and in aforesaid method [9-1] and [9-2], enumerate identical organic solvent.

When making the mixed solvent of water and organic solvent, the ratio of water can be preferably 5wt% or higher in the mixed solvent, and wherein 20～80wt% is for more preferably.[9-4] optionally, in conjunction with the be hydrolyzed methods of reaction of at least two kinds of methods among [9-1]～[9-3]

Its combination is had no particular limits.From the kind of desired resin, preparation facilities, suitable combination is selected in considerations such as reaction conditions.When not controlling swelling capacity, when promptly adopting method [9-3], the temperature of reaction system is preferably 5～100 ℃ usually, more preferably 10～60 ℃.By in conjunction with these methods, the swelling capacity of resin can be easily controlled, so that hydrolysis reaction carries out effectively, thereby obtains good resin.[9-5] consumption of water in hydrolysis reaction

Need carry out the crosslinking reaction of imide ring in the crosslinked polysuccinimide in the presence of water, the consumption of its water can be decided by needs.In each method of above-mentioned [9-1]～[9-4], the consumption of water is preferably 1～50 times of cross-linked poly-aspartic acid resin weight of generation usually, and wherein 1～20 times for more preferably.In method [9-1], the consumption of water also be decided by simultaneously water and can and water miscibles organic solvent between ratio.[9-6] is used for the alkaline reagents of hydrolysis reaction

To being used for making the be hydrolyzed alkaline reagents of reaction of crosslinked polysuccinimide imide ring to have no particular limits, but use a kind of alkaline aqueous solution usually.

The example of alkaline aqueous solution can comprise the aqueous solution of various use an alkali metal salts, this an alkali metal salt, for example alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali-metal carbonate such as yellow soda ash, salt of wormwood and Quilonum Retard, alkali-metal supercarbonate such as sodium bicarbonate and saleratus, alkali-metal acetate such as sodium acetate and potassium acetate and sodium oxalate; And ammoniacal liquor.Wherein, based on economic cost, sodium hydroxide and potassium hydroxide are preferred.They can be used alone or as a mixture.The pH value of [9-7] hydrolysis reaction system

The pH value of reaction mixture depends on the concentration of reagent such as alkaline aqueous solution in hydrolysis reaction.When suitably reducing the pH value, can prevent the fracture of molecular resin, consequently avoid reducing the water-absorbent of resin.If suitably increase the pH value, can accelerated reaction speed, thus the step of just carrying out is accomplished.Its pH value is preferably 7.5～13 usually, and more preferably 9～12.[10] swelling capacity is not carried out any adjusting and carry out the hydrolysis reaction of imide ring in the crosslinked polysuccinimide.

The front has been described each method under such situation: the imide ring in crosslinked polysuccinimide is hydrolyzed when reaction, the swelling capacity of reaction system is controlled in 3～100 times the scope.Aspect the water-absorbent and volumetric efficiency of cross-linked poly-aspartic acid resin, these methods can produce good effect.

Yet, it should be noted that, the present invention is not limited in the method for control swelling capacity in hydrolysis reaction, and it also comprises the above-mentioned crosslinked method that is in the polysuccinimide of dispersed, and the method for following washing cross-linked poly-aspartic acid resin gel, this gel is by water and/or can be with the miscible organic solvent hydrolysis of water and get.

When with regulate that the method to the liposoluble expansibility combines use in the hydrolysis reaction, these methods are more useful in practice.Yet, it should be noted that even swelling capacity is not carried out any control, these methods still can play the effect of himself when being hydrolyzed reaction.

When carrying out the hydrolysis reaction of the imide ring in the crosslinked polysuccinimide, each actual conditions is had no particular limits, as long as can open imide ring and can form carboxyl by alkaline hydrolysis by opening ring when not needing to control swelling capacity.Yet, preferably adopt above-mentioned under control swelling capacity situation, the condition of the preferred employing of institute when being hydrolyzed reaction.When not controlling molten length, the temperature of reaction system is preferably 5～100 ℃ usually, and wherein 10～60 ℃ for more preferably.[11] aftertreatment of cross-linked poly-aspartic acid resin

Aftertreatment for the cross-linked poly-aspartic acid resin that is got by the basic hydrolysis of imide ring in the crosslinked polysuccinimide has no particular limits.For example, optionally can handle or process, as neutralization, the interior exchange of salt, drying is purified granulating and surface-crosslinked.For neutralization, the interior exchange and the drying of salt will be described below.The neutralizing treatment of [11-1] cross-linked poly-aspartic acid resin

Optionally, can carry out neutralizing treatment to cross-linked poly-aspartic acid resin.Yet, it should be noted that the reaction mixture that contains cross-linked poly-aspartic acid resin behind the hydrolysis reaction is generally alkalescence.Therefore, preferably adding a kind of acid or analogue neutralizes.Through this neutralizing treatment, the carboxyl that is contained in the cross-linked poly-aspartic acid resin molecule can transform salify.Although this degree of neutralization is had no particular limits, based on asparagicacid residue numbers whole on the cross-linked poly-aspartic acid resin molecule, the ratio of the carboxyl that exists with its salt form can be preferably 0～50%, and wherein 0～30% for more preferably.

The method that neutralization is handled has no particular limits, but usually after hydrolysis reaction, adds a kind of acid and regulate its pH value.This sour object lesson can comprise the mineral acid example hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, carbonic acid and phosphoric acid; Carboxylic acid such as formic acid, acetate, propionic acid, oxalic acid and phenylformic acid; Sulfonic acid such as methylsulfonic acid, trifluoromethanesulfonic acid, Phenylsulfonic acid and toluenesulphonic acids; Phosphonic acids such as phosphenylic acid.Wherein, hydrochloric acid and sulfuric acid are preferred, and on expense and the easiness that removes, and hydrochloric acid is for more preferably.The interior exchange of the salt of [11-2] cross-linked poly-aspartic acid resin is handled

When the carboxyl in the cross-linked poly-aspartic acid resin molecule when neutralizing treatment changes salify, this salt can optionally change into dissimilar salt.

Example as the interior exchange reagent of salt can comprise an alkali metal salt, ammonium salt, amine salt etc.Concrete example can comprise an alkali metal salt such as sodium, potassium and lithium salts; Ammonium salt such as ammonium, tetramethylammonium, Tetrylammonium, tetrapropylammonium, tetrabutylammonium, 4 penta ammoniums, four own ammoniums, ethyl trimethyl ammonium, trimethylammonium propyl ammonium, butyl trimethyl ammonium, the amyl group trimethyl ammonium, hexyl trimethyl ammonium, cyclohexyl trimethyl ammonium, benzyltrimethylammon.um, triethyl propyl ammonium, triethyl butyl ammonium, triethyl amyl group ammonium, triethyl hexyl ammonium, cyclohexyl triethyl ammonium and benzyl triethyl ammonium ammonium; Amine salt such as Trimethylamine, triethylamine, tripropylamine, tributylamine, three amylamines, three hexyl amines, trolamine, tripropanol amine, three butanolamines, three amylalcohol amine, three hexanol amine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, dicyclohexylamine, dibenzyl amine, ethylmethylamine, methyl-propyl amine, butyl methyl amine, methyl amyl amine, the methyl hexyl amine, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, octylame, decyl amine, amino dodecane and cetylamine salt.

In these salt, what those had small molecular weight is preferred, and this is because the molecular weight that causes every monomeric unit of macromolecule increases relatively, and causes the water-absorbent of per unit weight to diminish thus.In addition, when the cross-linked poly-aspartic acid resin that generates may come in contact with people's skin or analogue, those had hypotoxic for preferred, for this reason, preferred sodium, potassium, the lithium of using, ammonium or triethanolamine salt, and from the angle of economy use sodium or sylvite for more preferably.The drying of [11-3] cross-linked poly-aspartic acid resin

Drying means to cross-linked poly-aspartic acid resin has no particular limits.For example, can comprise that conventional method as using hot-air dry, uses special steam drying, microwave drying, vacuum-drying, gas blower drying or in the presence of hydrophobic organic solvent, through the azeotropic dehydration drying.Drying temperature is preferably 20～200 ℃ usually, and wherein 50～120 ℃ for more preferably.

Can further handle exsiccant cross-linked poly-aspartic acid resin like this, as purifying, granulating, surface-crosslinked etc.[12] washing of cross-linked poly-aspartic acid resin

In the inventive method of preparation cross-linked poly-aspartic acid resin, make water and/or organic solvent that can be miscible with water, the gel of cross-linked poly-aspartic acid resin is washed or deposition again.

Through this method of purification, this cross-linked poly-aspartic acid resin all is improved on water-absorbent and gel-strength.It is believed that this should be owing to having removed water-soluble component such as monomer, oligopolymer and be contained in the resin gel and reduce the inorganic or organic salt of resin properties.

The object lesson of washing can comprise following two kinds of methods.

[12-1] makes water/or organic solvent that can be miscible with water, filters its gel, washing cross-linked poly-aspartic acid resin, this gel by water or a kind of water and can with the mixed solvent institute swelling of the miscible organic solvent of water.

[12-2] use can be miscible with water organic solvent, deposit its gel again, the washing cross-linked poly-aspartic acid resin, this gel oneself by water or a kind of water and can with the mixed solvent institute swelling of the miscible organic solvent of water.

For cross-linked poly-aspartic acid resin, using method [12-1] and [12-2] can isolating modes, mode that also can non-isolated, that is with a kind of wet cake, compacting cake, modes such as slurry.

Below with described method [12-1] and [12-2].[12-1] by making water/or organic solvent that can be miscible with water, filters and the method for detergent gel

According to the method, water and/or gel one this gel that can filter cross-linked poly-aspartic acid resin with the miscible organic solvent of water by water or a kind of water and can with the mixed solvent institute swelling of the miscible organic solvent of water, then, the water and/or the hydrogel that can obtain after filtration with the miscible organic solvent washing of water.Through filtering, the impurity littler than filter media sieve aperture can be filtered, and if desired, can remove wherein residual impurity by further washing.

To can having no particular limits of using with the miscible organic solvent of water, if it be can be miscible with water organic solvent.Concrete example can comprise alcohol as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, 2-methyl cellosolve and cellosolvo; Glycol such as ethylene glycol, glycol ether, triglycol, propylene glycol and dipropylene glycol; Ketone such as acetone, methylethylketone and methyl iso-butyl ketone (MIBK); Cyclic ethers such as tetrahydrofuran (THF) are with diox; N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), and tetramethylene sulfone.Methyl alcohol wherein, ethanol, propyl alcohol, Virahol and butanols are for preferred especially, and this is that after drying, solvent remains in the resin hardly because the cross-linked poly-aspartic acid resin that generates can be easily dry.

Cause the water of resin swelling and can have no particular limits being used to, need only their swelling resins fully with the consumption of water miscibles organic solvent.The swelling capacity of resin depends on the water-absorbent of resin.In this method, obtain swelling for preferred by using excessive distilled water or deionized water.Yet super excessively to make water be uneconomic.For this reason, the consumption of distilled water or deionized water can be preferred 0.001～10 times of distilled water that absorbs to resin or the weight of deionized water, wherein 0.02～5 times for more preferably.

Wash the water of swelling resin gel and/or can have no particular limits being used to the consumption of water miscibles organic solvent.Yet, from washing effect and economically, preferred consumption can 1～50 times to the weight of resin, wherein 3～20 times for more preferably.In addition, when with a kind of water with can wash the gel of swelling resin with the mixed solvent of the miscible organic solvent of water the time, from washing effect, their ratio is had no particular limits, however, wherein the ratio of water can be preferably 20wt% or higher.At this, a high proportion of organic solvent will cause the contraction of gel, as in method [12-2], and this resin formation redeposition state.

Although have no particular limits being used for filtering medium, includable example is the steel sieve, nonwoven nylon fiber, glass filter cloth etc.The size of mesh of strainer based on the sieve aperture of strainer, is preferably 50 μ m～1mm, and wherein 100 μ m～1mm are for more preferably.When the size of sieve aperture suitably increased, filtration velocity accelerated, and when sieve aperture suitably reduced, the rate of recovery of gel increased.

Filtration can be at filtering mixt be carried out under the static or condition of stirring.Filtration can also be further vibrate with strainer or rotation situation under carry out.Remove this, filtration can be carried out under normal pressure or elevated pressures, or under reduced pressure carries out suction strainer.

As the washing methods of this gel, gel can wash in due form, or gel can filter and wash by filtering gel, to obtain a kind of hydrogel, this hydrogel is distributed in distilled water or the deionized water, then, hydrogel is precipitated therein.Although comprise dispersion and carry out a large amount of steps of sedimentary method needs afterwards, it can obtain high detersive efficiency.

And the gel precipitation in filtration under the sieve aperture deposition is to the bottom, and therefore, this gel that precipitates can reclaim and use.

Gel with washing can so be dried after filtration, or can with the miscible organic solvent of water in precipitate, then, collect and dry sediment.

Although to being used for reppd can having no particular limits with the miscible organic solvent of water, common example can comprise alcohol as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, 2-methyl cellosolve and cellosolvo; Glycol such as ethylene glycol, glycol ether, triglycol, propylene glycol and dipropylene glycol; Ketone such as acetone, methylethylketone and methyl iso-butyl ketone (MIBK); Cyclic ethers such as tetrahydrofuran (THF) are with diox; N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, N, N '-dimethyl-imidazolinone, dimethyl sulfoxide (DMSO), and tetramethylene sulfone.Methyl alcohol wherein, ethanol, propyl alcohol, Virahol and acetone are for preferred especially, and this is because they can obtain by economic price.[12-2] can carry out reppd gel detergent method with the miscible organic solvent of water by using

According to the method, with oneself by water or a kind of water and can with the gel of the mixed solvent institute swollen cross-linked poly-aspartic acid resin of the miscible organic solvent of water pour into can with the miscible organic solvent of water in, this resin is carried out redeposition, or can be fed in the gel with its resin of redeposition with the miscible organic solvent of water.

Can carry out the swelling of cross-linked poly-aspartic acid resin with the same manner of aforesaid method [12-1].

When gel is poured into can with the miscible organic solvent of water in, when precipitating action takes place, optionally, can before pouring into, regulate the viscosity of gel.For example, when the ratio of the water in being contained in gel increases, the viscosity increased of its gel, on the contrary, and in the time can increasing with the ratio of the miscible organic solvent of water, the viscosity of its gel and become a kind of slurry.Yet, the mode or the timing of pouring into had no particular limits.When the slurry of gel or gel penetrate into can with the miscible organic solvent of water in the time, this gel is gathered into a kind of rigidity material in the process of infiltrating.In this case, preferably during infiltrating, carry out high-speed stirring, or at this material of the grinding machine for grinding of being furnished with the tool edge type stirring rake.

Be used for reppdly can comprising acetone, methylethylketone, methyl alcohol, ethanol with the miscible organic solvent example of water, propyl alcohol, butanols, hexanol, ethylene glycol, propylene glycol, 1,2-glycol dimethyl ether, methoxyl group methyl alcohol, 2-methyl cellosolve, tetrahydrofuran (THF) ， diox, N, N-dimethylamino methane amide, N, N-dimethylamino ethanamide, dimethyl sulfoxide (DMSO), N, N-dimethyl imide imidazolone, tetramethylene sulfone, and N-Methyl pyrrolidone.From industrialized angle, acetone wherein, methyl alcohol and ethanol are preferred, and this is because their high security and reclaiming easily.They can be used alone or as a mixture.Be used for sedimentary can with the miscible organic solvent of water can be used for resin swelling can be identical with the miscible organic solvent of water.If desired, it can contain water.

To being used for reppd can having no particular limits, as long as gel can redeposition (whole redeposition or gel redeposition) with the consumption of the miscible organic solvent of water.Its consumption can be preferably 0.5～10 times usually, and more preferably 1～5 times to the weight of resin, and its consumption also depends on solvent types.[13] preparation of the cross-linked poly-aspartic acid resin that need not wash

A kind of like this method has been described in the front, in this method, and gel, water and/or the organic solvent washing that can be miscible of the cross-linked poly-aspartic acid resin that gets by hydrolysis with water.This method can make cross-linked poly-aspartic acid resin aspect water-absorbent and gel-strength, has good effect.

Yet, on the angle of reality, if the present invention not only can carry out water and/or can with the miscible organic solvent washing of water or the method for redeposition cross-linked poly-aspartic acid resin, and can carry out aforesaid method and combine with the above-mentioned crosslinked method of the polysuccinimide that is in dispersed that makes, so, the present invention is more useful.Yet, not wash or redeposition even it should be noted that the gel of cross-linked poly-aspartic acid resin, a kind of method in back also can demonstrate the effect of itself.That is, above-mentioned washing or redeposition can optionally carry out, and depend on the application purpose of resin or to its required performance.[14] shape of cross-linked poly-aspartic acid resin

The object lesson of cross-linked poly-aspartic acid resin shape can comprise different shape, and is spherical as irregular pulverized powder, the grain shape, and particulate state, granulated particle, thin slice, bulk, the pearl shape, fine powder, fibrous, rod shape, film and sheet.According to application purpose, can select a kind of good shape.It also can be a kind of form of the material based on fiber, a kind of form of porous insert, a kind of form of foams, or a kind of form of granulate material.[15] size of particles of cross-linked poly-aspartic acid resin

Size of particles (median size) to cross-linked poly-aspartic acid resin has no particular limits, and can depend on application purpose and come the preferred particle size.For example, for disposable diaper, its mean sizes 100-1,000 μ m are preferred, and 150-600 μ m is for more preferably, and this is to have fast absorption rate and avoided gel blockage because wish it.Use as do water-proof material or for it during like purpose, its size 1-10 μ m is preferred when mediating with a kind of resin.Under the water holding material situation that is used for agricultural and gardening, consider its dispersiveness in soil, its size 100 μ m-5mm are preferred.[16] use-pattern of cross-linked poly-aspartic acid resin

Use-pattern to cross-linked poly-aspartic acid resin has no particular limits.It can use separately, or uses with other material mixing.

When crosslinked poly-aspartic acid resin and the use of other mixed with resin, it can be mediated in a kind of thermoplastic resin, carry out moulding by injection molding or similar approach then; It can mix with the formation monomer of other resin, if desired, can add initiator, and by light, heat or similar fashion are carried out polymerization then; It can disperse in solvent with other resin, casts afterwards and removes solvent; It can mix with the prepolymer of other resin, carries out crosslinked then; And it can with other mixed with resin, carry out crosslinked afterwards.

The moulding product of cross-linked poly-aspartic acid resin or the product that forms are in addition had no particular limits.It can solid matter, sheet, and film, fibrous, non-woven, forms such as foams rubber are used.And forming method or formation method to them have no particular limits.

Cross-linked poly-aspartic acid resin can itself or combine the matrix material mode that forms with other material and use.Although the structure to this matrix material has no particular limits, yet it can between non-woven or its analogue, form sandwich structure by remaining on pulp layer; It can form multilayered structure by using resin sheet or film as a kind of body material; Or it can form a kind of bilayer structure by in the resin sheet top casting.For example, form flaky cross-linked poly-aspartic acid resin a kind of superabsorbent sheet (comprising a kind of superabsorbent film) is provided.

And if desired, this cross-linked poly-aspartic acid resin also can mix with one or more other superabsorbent resins.If desired, also can add mineral compound, as salt, silica gel, white carbon black, superfine silicon dioxide and titanium dioxide powder; And organic compound, as the huge legendary turtle compound.And, also can with oxygenant, antioxidant, reductive agent, UV light absorber, antiseptic-germicide, sterilant, mould inhibitor, fertilizer, perfume, reodorant, pigment etc. mix.

Cross-linked poly-aspartic acid resin also can gel or the form of solid matter use.For example, make the water holding material when being used for agricultural and gardening, the life extender of clipping and carving, gel-type perfume compound, in the time of on the aspects such as gel-type reodorant, the mode that it can gel is used; And when as on the absorption agent of disposable diaper the time, it can the solid mode use.[17] application purpose of cross-linked poly-aspartic acid resin

Application purpose to cross-linked poly-aspartic acid resin has no particular limits.It can be used in the employed any Application Areas of conventional superabsorbent resin.

Typical application can comprise health product, as sanitary towel, and disposable diaper, brassiere and disposable rag; Medicinal product, as bandage, medicinal heelpiece and paste; Daily necessities, as the pet coverlet, portable urinal, gel-type perfume compound, gel-type reodorant, absorbing sweat fiber and disposable pocket well heater; Makeup, as shampoo, hair jelly and wetting agent; Agricultural and gardening product, as the water holding material in agricultural and the gardening, the life of clipping and carving prolongs agent, the profile (to the fixed base of clipping and carving) of flower, infanette, solution is cultivated the sheet material of vegetables, baby harness, fluidised cultivation medium and the agricultural sheet material of anti-dew; Packaging material for food is as Perserving materials and the dropping liquid absorbent sheet to food trays; The material that uses between the delivery period is as cold insulation body and the water absorbent sheet material that uses between the delivery period at fresh vegetables; Building and civil engineering material, as water-proof building material, the sealing material of civil engineering work and building, the leakage in the shield driving tunnel approach is bored liquid and is prevented agent, concrete additive, gasket and washer; The material that relates to electricity and electronics, as electronics and fibre-optic sealing material, the water-proof material of telecommunication cable and ink-jet copy paper; Material for water treatment is as the dewatering agent of sludge curing agent and gasoline and oil; The printing and dyeing sizing agent; Water-soluble bloated toy; Snowmaking; Slow release fertilizer; Sustained-release pesticides; Slow releasing pharmaceutical; The moisture control material; And static inhibitor.

Below, will the present invention more specifically be described by embodiment.Yet, it should be noted that the present invention is not limited in embodiment.Among below the embodiment and comparative example, all " parts " or " umber " mean " weight part " or " parts by weight ".

The water absorbability of every embodiment is measured by following tea-bag method.Wherein the gel-strength of every embodiment is measured by following steel ball laying method.In addition, the volumetric efficiency of the hydrolysis reaction of imide ring in each crosslinked polysuccinimide is represented (wt%) with the weight percent based on all wts of solvent that uses and crosslinked polysuccinimide.(1) tea bag method

Use distilled water and physiological saline as being absorbed liquid, water-absorbent is measured.Particularly, under the distilled water situation, about 0.05 part of superabsorbent polymkeric substance is encased in the tea-bag, this tea-bag makes (80mm * 50mm), and about 0.1 part of superabsorbent polymkeric substance is encased in the similar tea-bag by non-woven fabrics.Each tea-bag is immersed in the excessive respective liquid, and in this liquid, polymkeric substance carries out 1 hour swelling.Tea-bag is proposed then.Liquid drippage thereon is after 1 minute, and the weight that swollen polymer is contained in tea-bag is wherein measured.Only use an identical blank tea-bag,, similarly repeat above-mentioned steps as blank test.Be contained in the weight of tea-bag wherein with swollen polymer, deduct the weight of blank bag weight and superabsorbent polymkeric substance, the weight of superabsorbent polymkeric substance is divided by (more than draw) difference, and the numerical value of gained is as water-absorbent (gram/1 gram resin).By way of parenthesis, physiological saline is the sodium chloride aqueous solution of 0.9wt%.(2) steel ball laying method

Physiological saline (250 parts) is joined in 5 parts of superabsorbent resins, carry out 1 hour gelation then.On this gel, place steel ball one by one, from the minimum diameter steel ball, each placement is one on this gel.On this gel, can keep 30 seconds or longer and recessed maximum diameter steel ball goes on record, as the gel-strength of this gel.(A) in crosslinking reaction, relate to the embodiment that uses dispersion agent: [embodiment A 1]

7.2 part two hydrochloric acid lysine methyl esters and 22.6 part of one lysine hydrochloride are dispersed in 40 parts of distilled water.Dispersion liquid to generating adds 7.8 parts of caustic sodas bit by bit and neutralizes, thereby prepares a kind of lysine solution.In addition, 100 parts, weight-average molecular weight are 96,000 polysuccinimide, under nitrogen gas stream, are dissolved in 400 parts of N, in the dinethylformamide (hereinafter to be referred as " DMF "), then, add lysine solution.After so the mixture of preparation at room temperature stirred 30 minutes, add 400 parts of toluene as dispersion agent (poor solvent) to disperse polysuccinimide, then material reaction is 2 hours.After the reaction, reaction mixture is carried out suction strainer to collect a kind of throw out.This throw out toluene wash, then, drying is 2 hours under 60 ℃, thereby obtains a kind of crosslinked polysuccinimide.

Crosslinked polysuccinimide (120 parts) is dispersed in 400 parts of distilled water and the 400 parts of methanol mixture, then, in 2 hours, drips 130 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.The throw out that generates carries out drying under 60 ℃, thus, obtain 125 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 890 multiplying powers; Under the physiological saline situation, be 71 multiplying powers.[embodiment A 2]

37.6 a part lysine hydrochloride is dispersed in 80 parts of distilled water.Dispersion liquid to generating adds 10.3 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine solution.In addition, 100 parts, weight-average molecular weight are 96,000 polysuccinimide, under nitrogen gas stream, are dissolved among 400 parts of DMF, then, add lysine solution.After so the mixture of preparation at room temperature stirred 10 minutes, add 400 parts of methyl alcohol as dispersion agent (poor solvent) to disperse polysuccinimide, then material reaction is 20 hours.After the reaction, reaction mixture is carried out suction strainer to collect a kind of throw out.This throw out methanol wash, thus the wet cake of a kind of crosslinked polysuccinimide obtained.

The wet cake of crosslinked polysuccinimide is dispersed in 400 parts of distilled water and the 400 parts of methanol mixture, then, in 2 hours, drips 122.1 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 140 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

Cross-linked poly-aspartic acid under the distilled water situation, is 860 multiplying powers to the water-absorbent of fat; Under the physiological saline situation, be 70 multiplying powers.[embodiment A 3]

Except 3.0 parts of hexanediamines being used as linking agent solution in 10 parts of distilled water replaces the lysine solution, the mode of wet cake that obtains crosslinked polysuccinimide is with embodiment A 2.

Except the caustic soda aqueous solution that uses 148.8 parts of 27wt%,, the wet cake of crosslinked polysuccinimide is hydrolyzed in mode with embodiment A 2, neutralization, collect and drying, thus, obtain 108 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 880 multiplying powers; Under the physiological saline situation, be 70 multiplying powers.[embodiment A 4]

Except the dispersion liquid of 3.5 parts of m-xylene diamines in 20 parts of toluene that is used as linking agent replaces the lysine solution, the mode of the wet cake of the crosslinked polysuccinimide that obtains is with embodiment A 1 before drying.

Except the caustic soda aqueous solution that uses 148.8 parts of 27wt%,, the wet cake of crosslinked polysuccinimide is hydrolyzed in mode with embodiment A 2, neutralization, collect and drying, thus, obtain 110 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 760 multiplying powers; Under the physiological saline situation, be 65 multiplying powers.[embodiment A 5]

75.3 a part lysine hydrochloride is suspended in 150 parts of distilled water.Dispersion liquid to generating adds 40.6 parts of caustic sodas and neutralizes, thereby prepares a kind of Methionin suspension.In addition, 100 parts, weight-average molecular weight are that polysuccinimide and 500 parts of distilled water as dispersion agent (poor solvent) of 96,000 are fed in the super mixer of being furnished with the tool edge type stirring rake.With 15,000rpm decomposed polysuccinimide 1 hour, added the suspension of Methionin then, stirred at the mixture that so obtains, and reacted after 20 hours, added 500 parts of methyl alcohol, thereby obtained a kind of dispersion liquid of crosslinked polysuccinimide.

In crosslinked polysuccinimide dispersion liquid, in 2 hours, drip 13.7 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 95 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 460 multiplying powers; Under the physiological saline situation, be 63 multiplying powers.[embodiment A 6]

56.4 a part lysine hydrochloride is suspended in 100 parts of distilled water.Dispersion liquid to generating drips 25.5 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine solution.In addition, 100 parts, weight-average molecular weight are 96,000 polysuccinimide and 500 parts as the methanol feeding of dispersion agent (poor solvent) in the super mixer of being furnished with the tool edge type stirring rake.With 15,000rpm decomposed polysuccinimide 1 hour, added the suspension of Methionin then, after the mixture that so obtains stirs 20 hours, obtained a kind of dispersion liquid of crosslinked polysuccinimide.

In crosslinked polysuccinimide dispersion liquid, add 500 parts of distilled water, then, in 2 hours, drip 106.8 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 90 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 520 multiplying powers; Under the physiological saline situation, be 65 multiplying powers.[embodiment A 7]

48.0 part two hydrochloric acid lysine methyl esters are suspended in 80 parts of distilled water.Dispersion liquid to generating drips 16.5 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine methyl ester suspension.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, add 400 parts of methyl alcohol as dispersion agent (poor solvent) then, make polysuccinimide form dispersed.Lysine methyl ester suspension is joined in this dispersion liquid, at room temperature stirred then 20 hours.The mixture of this generation is collected a kind of throw out through suction strainer.With this throw out methanol wash, thereby obtain the wet cake of a kind of crosslinked polysuccinimide.

The wet cake of crosslinked polysuccinimide is dispersed in 400 parts of distilled water and the 400 parts of methanol mixture, then, in 2 hours, drips 122.1 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 98 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 450 multiplying powers; Under the physiological saline situation, be 64 multiplying powers.[embodiment A g]

7.2 part two hydrochloric acid lysine methyl esters and 22.6 part of one lysine hydrochloride are dissolved in 40 parts of distilled water.Dispersion liquid to generating drips 7.8 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine solution.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved in 400 parts of DMF and the 400 parts of mixed solvents as the methyl alcohol of dispersion agent (poor solvent), make polysuccinimide form dispersed.Lysine solution is joined in this dispersion liquid, at room temperature stirred then 40 hours.The mixture of this generation is collected a kind of throw out through suction strainer.With this throw out methanol wash, thereby obtain the wet cake of a kind of crosslinked polysuccinimide.

The wet cake of crosslinked polysuccinimide is dissolved in 400 parts of distilled water and the 400 parts of methanol mixture, then, in 2 hours, drips 130 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 94 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 660 multiplying powers; Under the physiological saline situation, be 67 multiplying powers.[embodiment A 9]

24.0 part two hydrochloric acid lysine methyl esters and 18.8 part of one lysine hydrochloride are dispersed in 40 parts of distilled water.Dispersion liquid to generating drips 12.4 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine solution.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, then, add lysine solution., after stirring 10 minutes under the room temperature, the mixture that generates joined in 30 minutes place that to be furnished with high-speed stirring oar and revolution be in 400 parts of toluene as dispersion agent (poor solvent) in 8,000 the mixing tank at the mixture that so obtains.Then reacted 10 hours, the mixture of this generation is collected a kind of throw out through suction strainer.With this throw out toluene wash, drying is 2 hours under 60 ℃, thereby obtains a kind of crosslinked polysuccinimide.

Crosslinked polysuccinimide (130 parts) is dispersed in 400 parts of distilled water and the 400 parts of methanol mixture, then, in 2 hours, drips 122.1 parts of 27wt% caustic soda aqueous solution.After dripping, this is generated mixture stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 125 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 620 multiplying powers; Under the physiological saline situation, be 65 multiplying powers.[Comparative examples A 1]

7.2 part two hydrochloric acid lysine methyl esters and 22.6 part of one lysine hydrochloride are dissolved in 40 parts of distilled water.Solution to generating drips 7.8 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine solution.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, then, add lysine solution.Stir under room temperature at the mixture that so obtains.In whipping process, reaction mixture generation thickening can not be carried out stirring again.Therefore, be reflected at and carried out under the no condition of stirring 30 minutes, thereby obtain a kind of reaction product in a kind of mode of gel.

The gel of reaction product is joined in 1,000 part of methyl alcohol, then the mixture that generates is at room temperature stirred.Because sedimentary particle is bigger, so can not increase stirring velocity.For the decomposition of whole cross-linking products, need the time more than a day, promptly this operation is difficult.Obtain a kind of throw out by suction strainer, then, elder generation washes with water with methyl alcohol again, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

The wet cake of crosslinked polysuccinimide is suspended in 15 parts of distilled water and the 15 parts of methanol mixture, drips 73 parts of 24wt% aqueous sodium hydroxide solutions then, makes the pH value of suspension drop to 11～12.After the pH value no longer reduced, adding dilute hydrochloric acid to the pH value of reaction mixture was 7.So the mixture that obtains is poured in 100 parts of methyl alcohol, and the throw out that generates is carried out drying and decomposition, thus, obtains 7.6 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 380 multiplying powers; Under the physiological saline situation, be 59 multiplying powers.[Comparative examples A 2]

Two hydrochloric acid lysine methyl esters (6 parts) are suspended among 200 parts of DMF, then with 6 parts of triethylamine neutralizations.50 parts of its weight-average molecular weight are that 130,000 the solution of polysuccinimide in 250 parts of DMF joins in this suspension.After the mixture of this generation at room temperature stirs 1 hour, drip 12 parts of triethylamines, at room temperature reacted then 40 hours.This reaction mixture is poured in the ethanol, collects the throw out that generates by filtering, and carries out drying then, obtains 50 parts of crosslinked polysuccinimides.

Crosslinked polysuccinimide (26 parts) is suspended in 5,000 parts of distilled water, then, drips the sodium hydroxide of 2N, and making the pH value is the hydrolysis reaction that 9～11 suspension carries out residual imide ring.Collect reaction mixture by filtering, carry out drying then, thus, obtain 86 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 110 multiplying powers; Under the physiological saline situation, be 30 multiplying powers.[to comparison and the discussion of embodiment A 1-A9 and Comparative examples A 1-A2]

Comparative examples A 1 relates to the ordinary method that a kind of preparation has the cross-linked poly-aspartic acid of high-hydroscopicity, and Comparative examples A 2 relates to the ordinary method of another kind of produced in high yields poly aspartic acid.Yet the result of Comparative examples A 1-A2 is not fine in all respects, and this is because they do not use any dispersion agent.More particularly, the productive rate of Comparative examples A 1 is quite low, and the water-absorbent of the resin of Comparative examples A 2 is obviously lower.

On the contrary, each all uses dispersion agent embodiment A 1-A9, carries out crosslinking reaction under the dispersed situation.Therefore, they are the produced in high yields cross-linked poly-aspartic acid resin respectively, and this resin demonstrates high-hydroscopicity.

Find out significantly from the front,, can bring useful effect the water-absorbent and the productive rate of resin by in crosslinking reaction, using a kind of dispersion agent and under the dispersed situation, carrying out the reaction of polysuccinimide.The embodiment of the crosslinking reaction when (B) water swelling degree is 3～100 times [Embodiment B 1]

Under nitrogen gas stream, 5 parts of its weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 20 parts of DMF, add 1.8 part of two hydrochloric acid lysine methyl ester and 3.1 parts of triethylamines then.After the mixture that generates at room temperature stirred 5 hours, stop to stir, reaction was carried out 50 hours.Methyl alcohol (100 parts) is joined in the reaction mixture, the mixture that generates is at room temperature stirred 2 hours to carry out redeposition, collect the throw out that generates by suction strainer, then, earlier with washing with water behind the methyl alcohol, thereby obtain a kind of wet cake of crosslinked polysuccinimide.

Should crosslinked polysuccinimide wet cake is suspended in 15 parts of distilled water and the 15 parts of methanol mixture, and under 3～100 times situation, it is 11～12 that the aqueous sodium hydroxide solution that adds 7.3 parts of 24wt% makes the pH value of suspension in the swelling capacity that keeps resin.When the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.So the mixture that obtains is poured in 100 parts the methyl alcohol, the throw out that generates is carried out drying and decomposition, thereby obtain 7.6 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 480 multiplying powers; Under the physiological saline situation, be 61 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 20.2%.[Embodiment B 2]

Except using its weight-average molecular weight is outside 155,000 the polysuccinimide, with the 146 parts of cross-linked poly-aspartic acid resins of method preparation with Embodiment B 1.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 550 multiplying powers; Under the physiological saline situation, be 63 multiplying powers.[Embodiment B 3]

To be suspended in the sodium chloride aqueous solution of 30 parts of 2wt% by wet cake as the crosslinked polysuccinimide that in Embodiment B 1, obtains, under 3～100 times situation, it is 11～12 that the aqueous sodium hydroxide solution of 8.6 parts of 24wt% of adding makes the pH value of suspension in the swelling capacity that keeps resin.When the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.So the mixture that obtains is poured in 100 parts the methyl alcohol, the throw out that generates is carried out drying and decomposition, thereby obtain 7.7 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 460 multiplying powers; Under the physiological saline situation, be 60 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 20.4%.[Embodiment B 4]

To be suspended in the mixed solvent of 25 parts of distilled water and 50 parts of Virahols by wet cake as the crosslinked polysuccinimide that obtains in Embodiment B 1, temperature wherein is 70 ℃.Under 3～100 times situation, it is 9～10 that the aqueous sodium hydroxide solution of 7.6 parts of 24wt% of adding makes the pH value of suspension in the swelling capacity that keeps resin.When the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.So the mixture that obtains is poured in 100 parts the methyl alcohol, the throw out that generates is carried out drying and decomposition, thereby obtain 7.2 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 460 multiplying powers; Under the physiological saline situation, be 60 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 12.6%.[Embodiment B 5]

Will be as the crosslinked polysuccinimide that in Embodiment B 1, obtains wet cake be suspended in the mixed solvent of the sodium chloride aqueous solution of 15 parts of 2wt% and 8 parts of methyl alcohol, under 3～100 times situation, it is 11～12 that the aqueous sodium hydroxide solution of 8.6 parts of 24wt% of adding makes the pH value of suspension in the swelling capacity that keeps resin.When the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.So the mixture that obtains is poured in 100 parts the methyl alcohol, the throw out that generates is carried out drying and decomposition, thereby obtain 7.6 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 480 multiplying powers; Under the physiological saline situation, be 61 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 24.8%.

Embodiment [B6]

Except using 0.15 part of hexanediamine to replace the two hydrochloric acid lysine methyl esters, with 7.0 parts of cross-linked poly-aspartic acid resins of method preparation with Embodiment B 1 as linking agent.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 380 multiplying powers; Under the physiological saline situation, be 59 multiplying powers.The volumetric efficiency of hydrolysis reaction is 18.9%.

Embodiment [B7]

As buck used in the hydrolysis reaction, replace the aqueous sodium hydroxide solution of 24wt% with the caustic soda aqueous solution of 8.2 parts of 30wt%, in addition with 7.9 parts of cross-linked poly-aspartic acid resins of method preparation with Embodiment B 1.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 450 multiplying powers; Under the physiological saline situation, be 58 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 18.9%.[comparative example B1]

To be suspended in 1000 parts of distilled water by wet cake as the crosslinked polysuccinimide that in Embodiment B 1, obtains.In the suspension that so obtains, it is 10～11 that the aqueous sodium hydroxide solution of dropping 8wt% makes the pH value of suspension.The caustic soda aqueous solution of adding 8% no longer reduces the pH value continuously.After the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.The mixture that so obtains is poured in 3000 parts the acetone, the throw out that generates carried out drying and decomposition, thereby obtain 7.7 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 180 multiplying powers; Under the physiological saline situation, be 38 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 0.8%.[comparative example B2]

To be suspended in the mixed solvent of 30 parts of distilled water and 90 parts of acetone by wet cake as the crosslinked polysuccinimide that in Embodiment B 1, obtains.In the suspension that so obtains, it is 10～11 that the aqueous sodium hydroxide solution of dropping 8wt% makes the pH value of suspension.The caustic soda aqueous solution of adding 8% no longer reduces the pH value continuously.After the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.The mixture that so obtains is poured in 3000 parts the acetone, the throw out that generates carried out drying and decomposition, thereby obtain 7.1 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 150 multiplying powers; Under the physiological saline situation, be 36 multiplying powers.And the volumetric efficiency of hydrolysis reaction is 5.6%.[to comparison and the discussion of Embodiment B 1-B7 and comparative example B1-B2]

In each comparative example B1-B2, be hydrolyzed reaction and the swelling capacity that need not control resin in 3～100 times scope, therefore, the water-absorbent of the cross-linked poly-aspartic acid resin that obtains is low, and the volumetric efficiency of hydrolysis reaction is low-down.

On the contrary, in each Embodiment B 1-B7, in 3～100 times scope, carry out the hydrolysis reaction of resin in the swelling capacity of controlling resin, therefore, the cross-linked poly-aspartic acid resin that obtains can demonstrate high water-absorbent, the volumetric efficiency height of hydrolysis reaction.

Find out significantly from top,, in 3～100 times of scopes, carry out imido hydrolysis reaction in the crosslinked polysuccinimide, can bring useful effect water-absorbent and volumetric efficiency in the swelling capacity that keeps resin in reaction system inside.(C) use is decomposed the crosslinked polysuccinimide that gets by gel is wet, and the embodiment of the reaction that is hydrolyzed in molten length is 3～100 times of scopes: [Embodiment C 1]

7.2 part two hydrochloric acid lysine methyl esters and 22.6 part of one lysine hydrochloride are dispersed in 40 parts of distilled water.Dispersion liquid to generating drips 7.8 parts of caustic sodas and neutralizes, thereby prepares a kind of lysine solution.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, then, add lysine solution., after stirring 1 hour under the room temperature, stop to stir at the mixture that so obtains, continue reaction 20 hours, obtain a kind of gel of crosslinked polysuccinimide.The gel of the crosslinked polysuccinimide that generates is fed in the mixing tank of being furnished with the tool edge type stirring rake, adds 400 parts of distilled water and 400 parts of methyl alcohol.Then, this gel carries out 5 minutes decomposition under 8000rpm.

Under 3～100 times of situations, in 2 hours, drip 129.7 parts of 27wt% caustic soda aqueous solution in the swelling capacity that keeps resin.After dripping, this material restir 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, add 300 parts of methyl alcohol again, stirred 1 hour.Collect the throw out that generates, then, under 60 ℃, carry out drying, thus, obtain 145 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 860 multiplying powers; Under the physiological saline situation, be 70 multiplying powers.[Embodiment C 2]

Except using its weight-average molecular weight is outside 155,000 the polysuccinimide, obtains 146 parts cross-linked poly-aspartic acid resin in the mode with Embodiment C 1.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 1050 multiplying powers; Under the physiological saline situation, be 72 multiplying powers.[Embodiment C 3]

Prepare a kind of lysine solution in the mode with Embodiment C 1, in addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, then, add lysine solution.In the reactor of being furnished with the vibration at high speed agitator, need not stir, at room temperature reacted 20 hours, obtain a kind of gel of crosslinked polysuccinimide.The gel of this crosslinked polysuccinimide decomposes in the reactor of being furnished with the vibration at high speed agitator.

400 parts of distilled water and 400 parts of methyl alcohol are joined in the reactor.Under 3～100 times of situations, in 2 hours, drip 129.7 parts of 27wt% caustic soda aqueous solution in the swelling capacity that keeps resin.After dripping, this material restir 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, add 300 parts of methyl alcohol again, collect the throw out that generates, then, under 60 ℃, carry out drying, thus, obtain 145 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 850 multiplying powers; Under the physiological saline situation, be 69 multiplying powers.[Embodiment C 4]

Except using the cross-linking agent aqueous solution that gets by 3.0 parts of hexanediamines to replace the two hydrochloric acid lysine methyl esters, obtain 136 parts cross-linked poly-aspartic acid resin in mode with Embodiment C 1.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 780 multiplying powers; Under the physiological saline situation, be 68 multiplying powers.[Embodiment C 5]

Except using the cross-linking agent aqueous solution that gets by 3.5 parts of m-xylene diamines to replace the two hydrochloric acid lysine methyl esters, obtain 132 parts cross-linked poly-aspartic acid resin in mode with Embodiment C 1.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 740 multiplying powers; Under the physiological saline situation, be 66 multiplying powers.[to comparison and the discussion of Embodiment C 1-C5]

In Embodiment C 1-C5, the cross-linked poly-aspartic acid resin that is obtained demonstrates high-hydroscopicity, this be because, as embodiment B1-B7, be in 3～100 scopes keeping its swelling capacity, the resin reaction that is hydrolyzed.This can obtain the cross-linked poly-aspartic acid resin of high-hydroscopicity, and this is because make the decomposition of wetting of the gel of crosslinked polysuccinimide.Otherwise in Comparative examples A 1, its productive rate is quite low, and in Comparative examples A 2, its water-absorbent reduces significantly.(D) with lysine salt and/or ornithine salt embodiment [embodiment D1] as linking agent

37.6 a part lysine hydrochloride is dispersed in 80 parts of distilled water.Dispersion liquid to generating drips 9.5 parts of caustic sodas and neutralizes, thereby prepares a kind of Methionin/Sodium lysinate salt brine solution.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, then, add lysine solution.After stirring 10 minutes under the room temperature, dispersion liquid is added 400 parts of methyl alcohol as dispersion agent (poor solvent) at the mixture that so obtains, reacted then 20 hours.After the reaction, reaction mixture is carried out suction strainer and obtains throw out.This throw out washs with methyl alcohol, obtains a kind of wet cake of crosslinked polysuccinimide.

The wet cake of crosslinked polysuccinimide is dispersed in 400 parts of distilled water and the 400 parts of methanol mixture, then, in 2 hours, drips 122 parts of 27wt% caustic soda aqueous solution.After dripping, this generates mixture and stirred 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, this mixture is poured in 300 parts of methyl alcohol, stirred 1 hour.Collect the throw out that generates by filtering, then, under 60 ℃, carry out drying, thus, obtain 140 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 920 multiplying powers; Under the physiological saline situation, be 74 multiplying powers.[embodiment D2]

9.4 a part lysine hydrochloride is dispersed in 20 parts of distilled water.Dispersion liquid to generating drips 2.1 parts of caustic sodas and neutralizes, thereby prepares a kind of Sodium lysinate salt brine solution.In addition, under nitrogen gas stream, 100 parts, weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 400 parts of DMF, then, add the Sodium lysinate aqueous solution., stop to stir at the mixture that so obtains after stirring 1 hour under the room temperature, reaction is proceeded 20 hours.Obtain a kind of gel of crosslinked polysuccinimide.The gel of this crosslinked polysuccinimide enters into the mixing tank of being furnished with the tool edge type stirring rake.400 parts of distilled water and 400 parts of methyl alcohol are joined in the mixing tank.Then, gel decomposed under 8000rpm 5 minutes.

Under 3～100 times of situations, in 2 hours, drip 145.0 parts of 27wt% caustic soda aqueous solution in the swelling capacity that keeps resin.After dripping, this material restir 2 hours.Use the hydrochloric acid soln of 7wt%, with the mixture pH=7 that neutralizes.After the neutralization, add 300 parts of methyl alcohol again, collect the throw out that generates, then, under 60 ℃, carry out drying, thus, obtain 131 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 860 multiplying powers; Under the physiological saline situation, be 70 multiplying powers.[to the discussion of embodiment D1-D2]

In embodiment D1, the cross-linked poly-aspartic acid resin that is obtained demonstrates high-hydroscopicity, and this is because as embodiment A1-A9, use dispersion agent and carry out crosslinking reaction under the dispersed situation.In embodiment D2, the cross-linked poly-aspartic acid resin that is obtained also demonstrates high-hydroscopicity, this be because, as embodiment B1-B7, be in 3～100 scopes keeping its swelling capacity, the resin reaction that is hydrolyzed.

And owing to use lysine salt as linking agent, embodiment D1-D2 can provide the cross-linked poly-aspartic acid resin that always has high security.(E) embodiment of washing cross-linked poly-aspartic acid resin gel: [embodiment E 1]

Under nitrogen gas stream, 5 parts of its weight-average molecular weight are that 96,000 polysuccinimide is dissolved among 20 parts of DMF, add 1.8 part of two hydrochloric acid lysine methyl ester and 3.1 parts of triethylamines then.After the mixture that generates at room temperature stirs 20 hours, methyl alcohol (100 parts) is joined in the reaction mixture, the mixture that generates at room temperature stirs 2 hours to decompose the gel that generates, collect the throw out that generates by suction strainer, then, earlier with washing with water behind the methyl alcohol, thereby obtain a kind of wet cake of crosslinked polysuccinimide.

Should crosslinked polysuccinimide wet cake is suspended in 30 parts of distilled water and the 90 parts of methanol mixture, and it is 11～12 that the aqueous sodium hydroxide solution that adds 8wt% makes the pH value of suspension.Add this basic solution the pH value is no longer reduced, when the pH value no longer reduced, the hydrochloric acid that adds dilution was 7 up to the pH of reaction mixture value.Distilled water (50 parts) is joined in the throw out of generation to cause gelation, filter, collect the gel that so obtains by filter sieve with 425 μ m sieve apertures.Thoroughly wash with distilled water, carry out drying then, thereby obtain 6.9 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 490 multiplying powers; Under the physiological saline situation, be 62 multiplying powers.And the intensity of gel is 20/16 inch.[embodiment E 2]

Identical with the method for embodiment E 1, crosslinked polysuccinimide is hydrolyzed, then neutralization.After this, add 15 parts of distilled water and 15 parts of methyl alcohol, make the throw out gelation of generation.Filter by filter sieve, collect the gel that so obtains with 200 μ m sieve apertures.With 15 parts of 50wt% methanol aqueous solution washings twice, carry out drying then, thereby obtain 7.2 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 550 multiplying powers; Under the physiological saline situation, be 64 multiplying powers.And the intensity of gel is 20/16 inch.[embodiment E 3]

Identical with the method for embodiment E 1, crosslinked polysuccinimide is hydrolyzed, then neutralization.After this, 15 parts of distilled water and 18 parts of methyl alcohol are joined in the throw out of generation, cause gelation in a kind of mode of slurry.In 30 minutes, the gel that generates is joined in 50 parts of methyl alcohol bit by bit, make gel carry out redeposition.Collect the throw out that so obtains.Carry out drying then, thereby obtain 7.7 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 450 multiplying powers; Under the physiological saline situation, be 61 multiplying powers.And the intensity of gel is 20/16 inch.[Comparative Example E 1]

Identical with the method for embodiment E 1, crosslinked polysuccinimide is hydrolyzed, then neutralization.After this, the throw out of generation carries out drying under 60 ℃, grinds then, thereby obtains 7.6 parts of cross-linked poly-aspartic acid resins as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 160 multiplying powers; Under the physiological saline situation, be 37 multiplying powers.And the intensity of gel is 8/16 inch.[to the comparison and the discussion of embodiment E 1-E3 and Comparative Example E 1]

Comparative Example E 1 has provided the gel-strength of low water absorbable and difference, and this is because the cause that the gel of employed cross-linked poly-aspartic acid resin does not wash.

In contrast, each among the embodiment E 1-E3 is all prepared the cross-linked poly-aspartic acid resin with high-hydroscopicity and good gel-strength, and this is because the gel of cross-linked poly-aspartic acid resin was washed.

As from top clear and definite, when by hydrolysis cross-linked poly-aspartic acid resin, water and/or can be with the miscible organic solvent washing of water the time will produce beneficial effect to its water-absorbent and gel-strength.(F) preparation has the embodiment of the resin of high absorption speed

Among each embodiment, with same step, to be absorbed as 10 minutes (W10) of distilled water, its shared per-cent is calculated in the absorption with respect to 1 hour (W60) below, and the result is the index of absorption speed as a comparison.In addition, consider that the cause owing to size of particles causes different absorption speeds, therefore, the resin that is used to measure screens its size of particles only in 100～500 mu m ranges.[embodiment F 1]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 2.78g (0.015mol), the aqueous sodium hydroxide solution that adds 2.44g (0.015mol) 24.5wt% then neutralizes.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture of generation reacted 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, then, under 25 ℃, carry out ageing 3 hours.Then, (1.63g 0.01mol), carried out crosslinking reaction 20 hours under 25 ℃ to drip the 24.5wt% aqueous sodium hydroxide solution.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.The aqueous solution of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, is to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.To reaction when finishing, consume the aqueous sodium hydroxide solution 13.8g (0.085mol) of 24.5wt% and 3 hours.In the reactant of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 10.5g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 1,090 multiplying power; Under the physiological saline situation, be 96 multiplying powers.

And W10/W60 * 100 are 60.2%.[embodiment F 2]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 2.78g (0.015mol), the aqueous sodium hydroxide solution that adds 2.44g (0.015mol) 24.5wt% then neutralizes.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture of generation reacted 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, then, under 25 ℃, carry out ageing 3 hours.Then, (2.44g 0.015mol), carried out crosslinking reaction 20 hours under 25 ℃ to drip the 24.5wt% aqueous sodium hydroxide solution.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution 13.5g (0.083mol) of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.The reaction mixture that generates was carried out ageing 1 hour.In the reactant of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 12.3g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 690 multiplying powers; Under the physiological saline situation, be 75 multiplying powers.

And W10/W60 * 100 are 75.9%.[embodiment F 3]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 3.70g (0.020mol), the aqueous sodium hydroxide solution that adds 3.27g (0.020mol) 24.5wt% then neutralizes.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture of generation reacted 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, then, under 25 ℃, carry out ageing 3 hours.Then, (1.63g 0.010mol), carried out crosslinking reaction 20 hours under 25 ℃ to drip the 24.5wt% aqueous sodium hydroxide solution.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution 13.5g (0.083mol) of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.The reaction mixture that generates was carried out ageing 1 hour.In the reactant of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 12.3g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 600 multiplying powers; Under the physiological saline situation, be 83 multiplying powers.

And W10/W60 * 100 are 61.9%.[embodiment F 4]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 4.63g (0.025mol), the aqueous sodium hydroxide solution that adds 4.08g (0.025mol) 24.5wt% then neutralizes.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture of generation reacted 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, then, under 25 ℃, carry out ageing 3 hours.Then, (1.63g 0.010mol), carried out crosslinking reaction 20 hours under 25 ℃ to drip the 24.5wt% aqueous sodium hydroxide solution.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution 13.5g (0.083mol) of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.The reaction mixture that generates was carried out ageing 1 hour.In the reactant of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 14.8g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 450 multiplying powers; Under the physiological saline situation, be 48 multiplying powers.

And W10/W60 * 100 are 62.7%.[embodiment F 5]

To be same as the step of embodiment F 1, obtain the wet cake of crosslinked polysuccinimide.

This wet cake is suspended in the 120g methyl alcohol.To dissolve 7.73g (0.1mol) glycine and the glycine solution of 4.2g sodium hydroxide in 30g distilled water is added drop-wise in this suspension, then, 25 ℃ of reactions 24 hours down.Then, with the aqueous hydrochloric acid neutralization of 9wt%, making pH is 7.5.By filtering the collecting precipitation thing, wash, dry then, thus obtaining the glycine derivative of 18.1g as the crosslinked polysuccinimide of superabsorbent polymer, glycine wherein is introduced into as side group.

The water-absorbent of crosslinked polysuccinimide derivative under the distilled water situation, is 720 multiplying powers; Under the physiological saline situation, be 79 multiplying powers.

And W10/W60 * 100 are 75.5%.[embodiment F 6]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 2.78g (0.015mol), the aqueous sodium hydroxide solution that adds 4.08g (0.025mol) 24.5wt% then neutralizes.This solution is dissolved in the 38.8g methyl alcohol, in 1 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture of generation reacted under 25 ℃ 10 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.The aqueous solution of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, is to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.Till finishing to reaction, consume aqueous sodium hydroxide solution 13.1g and cost 4 hours the time of 24.5wt% altogether.Adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 13.3g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 480 multiplying powers; Under the physiological saline situation, be 51 multiplying powers.

And W10/W60 * 100 are 92.7%.[embodiment F 7]

Except its crosslinking time changed over 5 hours, prepare a kind of wet cake of crosslinked polysuccinimide by the step of embodiment F 6.

Should be hydrolyzed in the mode that is same as embodiment F 6 by wet cake, obtain the cross-linked poly-aspartic acid resin of 11.1g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 600 multiplying powers; Under the physiological saline situation, be 60 multiplying powers.

And W10/W60 * 100 are 91.1%.[embodiment F 8]

In the distilled water of 2.0g, the lysine hydrochloride of dissolving 3.70g (0.020mol), the aqueous sodium hydroxide solution that adds 4.90g (0.030mol) 24.5wt% then neutralizes.This solution is dissolved in the 38.8g methyl alcohol, in 1 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture of generation reacted under 25 ℃ 10 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution 13.1g of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11 at 25-35 ℃ and pH.The reaction mixture of Sheng Chenging carried out ageing 1 hour then.In the mixture of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 14.0g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 310 multiplying powers; Under the physiological saline situation, be 43 multiplying powers.

And W10/W60 * 100 are 93.5%.[embodiment F 9]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 2.78g (0.015mol), the aqueous sodium hydroxide solution that adds 4.08g (0.025mol) 24.5wt% then neutralizes.In 0.5 hour, it is that 96,000 polysuccinimide is in the solution of 38.8gDMF, after this that the solution that generates and 12.9g methyl alcohol are added drop-wise to its weight-average molecular weight of 9.71g (0.10mol) from different inlets, add 25.9g methyl alcohol, under 25 ℃, carried out crosslinking reaction 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.The aqueous solution of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, is to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.Then the reaction mixture that generates was carried out ageing 1 hour.Till no longer changing to pH, need 3 hour time.This mixture carries out ageing 1 hour then.In the mixture of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 12.7g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 580 multiplying powers; Under the physiological saline situation, be 60 multiplying powers.

And W10/W60 * 100 are 93.5%.[embodiment F 10]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 2.78g (0.015mol), the aqueous sodium hydroxide solution that adds 4.08g (0.025mol) 24.5wt% then neutralizes.This solution is dissolved in the 38.8g methyl alcohol.In 1 hour, it is that 96,000 polysuccinimide is in the solution of 38.8gDMF that the drips of solution that generates is added to its weight-average molecular weight of 9.71g (0.10mol).The mixture of this generation carried out crosslinking reaction 10 hours under 25 ℃.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in the 116.5g methanol mixture.In this suspension, drip through dissolve the glycine solution that 7.73g (0.1mol) glycine and 4.2g sodium hydroxide form in 30g distilled water, reacted 24 hours down at 25 ℃ then.Making pH with the neutralization of the aqueous hydrochloric acid of 9wt% then is 7.5, by filtering the collecting precipitation thing, washing, drying then, thereby obtain the glycine derivative of 18.8g as the crosslinked polysuccinimide of superabsorbent polymer, glycine is wherein introduced as side group.

The water-absorbent of crosslinked polysuccinimide derivative under the distilled water situation, is 490 multiplying powers; Under the physiological saline situation, be 53 multiplying powers.

And W10/W60 * 100 are 92.1%.[embodiment F 11]

Except replacing the lysine hydrochloride with 1.74g (0.02mol) hexanediamine, repeat the step of embodiment F 6, obtain the cross-linked poly-aspartic acid resin of 10.5g as superabsorbent polymer.

The water-absorbent of crosslinked polysuccinimide derivative under the distilled water situation, is 61 multiplying powers; Under the physiological saline situation, be 25 multiplying powers.

And order, W10/W60 * 100 are 95.2%.[embodiment F 12]

In the distilled water of 1.0g, dissolve the lysine hydrochloride of 1.85g (0.01mol), add the capable neutralization of aqueous sodium hydroxide solution of 1.64g (0.01mol) 24.5wt% then.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture reaction of generation 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, then, add the aqueous sodium hydroxide solution of 1.64g (0.01mol) 24.5wt%, under 25 ℃, carried out crosslinking reaction 3 hours.In addition, in the distilled water of 1.0g, the lysine hydrochloride of dissolving 0.93g, the aqueous sodium hydroxide solution that adds 1.64g (0.01mol) 24.5wt% then neutralizes.In 0.5 hour, this drips of solution is added in the mixture of crosslinking reaction, then 25 ℃ of following ageings 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.The aqueous solution of the sodium hydroxide of 24.5wt% is added drop-wise in this suspension, is to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.Till finishing to reaction, consume aqueous sodium hydroxide solution 13.8g and cost 3 hours the time of 24.5wt% altogether.Adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 12.5g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 520 multiplying powers; Under the physiological saline situation, be 65 multiplying powers.

And W10/W60 * 100 are 70.1%.[embodiment F 13]

In the distilled water of 1.0g, the lysine hydrochloride of dissolving 1.85g (0.01mol), the aqueous sodium hydroxide solution that adds 1.64g (0.01mol) 24.5wt% then neutralizes.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture reaction of generation 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, then, add the aqueous sodium hydroxide solution of 0.82g (0.005mol) 24.5wt%, under 25 ℃, carried out crosslinking reaction 3 hours.In addition, in the distilled water of 1.0g, the lysine hydrochloride of dissolving 0.93g (0.005mol), the aqueous sodium hydroxide solution that adds 1.64g (0.01mol) 24.5wt% then neutralizes.In 0.5 hour, this drips of solution is added in the mixture of crosslinking reaction, then 25 ℃ of following ageings 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution of the sodium hydroxide of 13.5g (0.083mol) 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.The reaction mixture that generates carried out ageing 1 hour.Adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 11.3g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 537 multiplying powers; Under the physiological saline situation, be 69 multiplying powers.

And W10/W60 * 100 are 71.7%.[embodiment F 14]

In the distilled water of 1.0g, the lysine hydrochloride of dissolving 0.56g (0.003mol) adds in the aqueous sodium hydroxide solution of 0.98g (0.006mol) 24.5wt% and hydrochloric acid then.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture reaction of generation 30 minutes.After this, add 38.8g methyl alcohol and make reaction system form dispersed, in addition, in the distilled water of 1.0g, the lysine hydrochloride of dissolving 2.24g (0.012mol), the aqueous sodium hydroxide solution that adds 3.92g (0.024mol) 24.5wt% then neutralizes.In 0.5 hour, this drips of solution is added in the mixture of crosslinking reaction, then 25 ℃ of following ageings 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution of the sodium hydroxide of 13.5g (0.083mol) 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.The reaction mixture of Sheng Chenging carried out ageing 1 hour then.In the mixture of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 12.8g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 452 multiplying powers; Under the physiological saline situation, be 57 multiplying powers.

And W10/W60 * 100 are 83.3%.[embodiment F 15]

In the distilled water of 1.0g, the lysine hydrochloride of dissolving 0.56g (0.003mol) adds in the aqueous sodium hydroxide solution of 0.98g (0.006mol) 24.5wt% and hydrochloric acid then.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture reaction of generation 30 minutes.In addition, in the distilled water of 1.0g, the lysine hydrochloride of dissolving 2.24g (0.012mol), the aqueous sodium hydroxide solution that adds 3.92g (0.024mol) 24.5wt% then neutralizes.This solution and 38.8g methanol mixed.In 0.5 hour, this drips of solution is added in the mixture of crosslinking reaction, then 25 ℃ of following ageings 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 83.1g water and the 116.5g methanol mixture.In 3 hours, the aqueous solution of the sodium hydroxide of 13.5g (0.083mol) 24.5wt% is added drop-wise in this suspension, be to be hydrolyzed under the situation of 9-11.5 at 25-35 ℃ and pH.The reaction mixture of Sheng Chenging carried out ageing 1 hour then.In the mixture of so hydrolysis, adding hydrochloric acid is 7-7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 14.8g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 600 multiplying powers; Under the physiological saline situation, be 71 multiplying powers.

And W10/W60 * 100 are 91.3%.[embodiment F 16]

In the distilled water of 1.0g, the lysine hydrochloride of dissolving 1.85g (0.01mol) adds in the aqueous sodium hydroxide solution of 1.64g (0.01mol) 24.5wt% and hydrochloric acid then.In 0.5 hour, with the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, the mixture reaction of generation 1 hour.After this, add 38.8g methyl alcohol and make reaction system form dispersed, add the aqueous sodium hydroxide solution of 1.64g (0.01mol) 24.5wt%, under 25 ℃, carried out crosslinking reaction 3 hours.In addition, in the distilled water of 1.0g, the lysine hydrochloride of dissolving 0.93g (0.005mol), the aqueous sodium hydroxide solution that adds 1.64g (0.01mol) 24.5wt% then neutralizes.In 0.5 hour, this drips of solution is added in the mixture of crosslinking reaction, then 25 ℃ of following ageings 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in the 116.5g methanol mixture.In this suspension, drip through dissolve the glycine solution that 7.73g (0.1mol) glycine and 4.2g sodium hydroxide form in 30g distilled water, reacted 24 hours down at 25 ℃ then.Making pH with the neutralization of the aqueous hydrochloric acid of 9wt% then is 7.5, by filtering the collecting precipitation thing, washing, drying then, thereby obtain the glycine derivative of 18.8g as the crosslinked polysuccinimide of superabsorbent polymer, glycine is wherein introduced as side group.

The water-absorbent of crosslinked polysuccinimide derivative under the distilled water situation, is 492 multiplying powers; Under the physiological saline situation, be 51 multiplying powers.

And W10/W60 * 100 are 86.3%.[Comparative Example F 1]

In the distilled water of 1.5g, the lysine hydrochloride of dissolving 2.78g (0.015mol), the aqueous sodium hydroxide solution that adds 4.08g (0.025mol) 24.5wt% then neutralizes.In 0.5 hour, it is that 96,000 polysuccinimide is in the solution of 38.8gDMF that the drips of solution that generates is added to its weight-average molecular weight of 9.71g (0.10mol).In the process that adds, viscosity constantly increases, and reaction mixture gel fully, to such an extent as to can not stir again.After this, under no condition of stirring, reaction mixture carries out ageing 30 hours under 25 ℃.In the gel that methyl alcohol (100g) add is generated so that its decompose.Yet, because the difficulty that stirs is decomposed whole gels and is needed about 20 hours.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in 90g water and the 120g methanol mixture.At 25-35 ℃ and pH is under the situation of 9-11 the aqueous solution of the sodium hydroxide of 13.1g 24.5wt% to be added drop-wise in this suspension, is hydrolyzed then.Because its throw out has big size of particles, speed of response is slow, and hydrolysis needs about 6 hours.The aqueous hydrochloric acid that adds 9wt% then is 7.5 to regulate pH, collects the throw out of generation by decant.In the throw out that so obtains, add entry (20g) and make this throw out change into slurry.This slurry is poured in the 200g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 8.8g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 400 multiplying powers; Under the physiological saline situation, be 53 multiplying powers.

And W10/W60 * 100 are 60.7%.[Comparative Example F 2]

It is that 96,000 polysuccinimide is in the solution of 38.8gDMF that the hexanediamine of 1.74g (0.015mol) is joined its weight-average molecular weight of 9.71g (0.10mol).After 5 minutes, the whole gels of reaction mixture.Make the preservation of spending the night of this gel, consequently DMF oozes out from gel.Gel is separated, use methanol wash, dry then, obtain a kind of crosslinked polysuccinimide.

In shredder, the polymkeric substance grind into powder with so obtaining then, is suspended in 90g water and the 120g methanol mixture.At the aqueous solution of the sodium hydroxide that passes through adding 24.5wt%, control pH is under the situation of 9-11, and reaction is hydrolyzed.This reaction needed 50 hours.The hydrolysed mix that so obtains is poured in the 500g methyl alcohol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 3.5g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 22 multiplying powers; Under the physiological saline situation, be 10 multiplying powers.

And W10/W60 * 100 are 78.6%.[Comparative Example F 3]

In the DMF of 100g, the two hydrochloric acid lysine methyl esters of suspension 3.50g (0.015mol), the triethylamine with equimolar amount neutralizes then.With the drips of solution that generates be added to its weight-average molecular weight of 9.71g (0.10mol) be 96,000 polysuccinimide in the solution of 38.8gDMF, stirred then 1 hour.(3.03g, 0.030mol), crosslinking reaction was carried out under 25 ℃ 40 hours then to add triethylamine.Reaction mixture poured into carry out redeposition in the 300g methyl alcohol.The throw out of collection generation is washed then after filtration, thereby obtains a kind of wet cake of crosslinked polysuccinimide.

This wet cake is suspended in the 2000g water.Making pH at the aqueous solution of the sodium hydroxide that drips 24.5wt% is under the situation of 9-11, is hydrolyzed.This reaction mixture (flowable gel) is poured in the 500ml ethanol to carry out redeposition.By filtering the collecting precipitation thing, wash, dry then, thus obtain the cross-linked poly-aspartic acid resin of 12.8g as superabsorbent polymer.

The water-absorbent of cross-linked poly-aspartic acid resin under the distilled water situation, is 110 multiplying powers; Under the physiological saline situation, be 30 multiplying powers.

And W10/W60 * 100 are 61.2%.[to comparison and the discussion of embodiment F 1-F16 and Comparative Example F 1-F3]

In Comparative Example F 1, the cross-linked poly-aspartic acid resin that obtains through hydrolysis has sufficiently high water-absorbent, but its operability is relatively poor, and consequently productive rate is low.

In Comparative Example F 2, the non-constant of its operability.Through hydrolysis and cross-linked poly-aspartic acid resin only demonstrate unpractical very reduced water absorption.

In Comparative Example F 3, attempt a kind of crosslinked polysuccinimide of produced in high yields, but consequently, through hydrolysis and the cross-linked poly-aspartic acid resin water-absorbent that only can obtain to reduce.

In contrast, each among the embodiment F 1-F16 all can high yield obtain cross-linked poly-aspartic acid resin, and this resin has high-hydroscopicity, and demonstrates and have good absorption speed.

Claims (12)

1. one kind by making the reaction that is hydrolyzed of imide ring in the crosslinked polysuccinimide prepare method of cross-linked poly-aspartic acid resin, and wherein this hydrolysis reaction is to carry out under 3～100 times the situation in the swelling capacity of controlling the reaction system resin.

2. the process of claim 1 wherein that this hydrolysis reaction carries out a kind of can being contained in wherein the aqueous solution with the miscible organic solvent of water.

3. the method for claim 2, wherein, in this reaction system, the swelling capacity of this resin is by the Polarity Control that can be contained in this aqueous solution wherein with the miscible organic solvent of water.

4. the process of claim 1 wherein that this hydrolysis reaction carries out in a kind of inorganic salt and/or a kind of organic salt are contained in wherein the aqueous solution.

5. the method for claim 4, wherein, in this reaction system, the swelling capacity of this resin is by controlling by changing the osmotic pressure that these inorganic salt and/or organic salt is contained in reaction system wherein.

6. the process of claim 1 wherein that this hydrolysis reaction carries out in a kind of 40～100 ℃ solvent.

7. the method for claim 6 wherein, changes the water-absorbent of resin in this reaction system by the temperature that changes this solvent, thereby controls the swelling capacity of this resin in this reaction system.

8. the process of claim 1 wherein the preparation of this crosslinked polysuccinimide, is to be carried out with gel that the linking agent reaction gets in solvent by polysuccinimide by wet lapping is a kind of.

9. the process of claim 1 wherein the preparation of this crosslinked polysuccinimide, is to be undertaken by polysuccinimide and a kind of alkaline aminocarboxylic acid reactant salt as linking agent.

10. the process of claim 1 wherein the preparation of this crosslinked polysuccinimide, is to be undertaken by a kind of polysuccinimide and reaction of a kind of linking agent that is dispersed by dispersion agent.

11. the method for claim 1, comprise make water and/or can with the gel of the cross-linked poly-aspartic acid resin of miscible organic solvent washing of water or redeposition charging.

12. the process of claim 1 wherein that this crosslinked polysuccinimide is that a kind of its surface is highly cross-linked particulate forms.